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Next generation immunotherapy: improving stemness of polyclonal Big t cells to enhance anti-tumor activity.
We use Kelvin probe force microscopy (KPFM) to probe the carrier-dependent potential of an electrostatically defined quantum dot (QD) in a graphene/hexagonal boron nitride (hBN) heterostructure. We show that gate-dependent measurements enable a calibration scheme that corrects for uncertainty inherent in typical KPFM measurements and accurately reconstructs the potential well profile. Our measurements reveal how the well changes with carrier concentration, which we associate with the nonlinear dependence of graphene's work function on carrier density. These changes shift the energy levels of quasi-bound states in the QD which we can measure via scanning tunneling spectroscopy (STS). We show that the experimentally extracted energy levels closely compare with wave functions calculated from the reconstructed KPFM data. This methodology, where KPFM and STS data are simultaneously acquired from 2D materials, allows the quasiparticle response to an electrostatic potential to be determined in a self-consistent way.The allotropic affinity for bulk silicon and unique electronic and optical properties make silicene a promising candidate for future high-performance devices compatible with mature complementary metal-oxide-semiconductor technology. selleck However, silicene's outstanding properties are not preserved on its most prominent growth templates, due to strong substrate interactions and hybridization effects. In this letter, we report the optical properties of silicene epitaxially grown on Au(111). A novel in situ passivation methodology with few-layer hexagonal boron nitride enables detailed ex situ characterization at ambient conditions via μ-Raman spectroscopy and reflectance measurements. The optical properties of silicene on Au(111) appeared to be in accordance with the characteristics predicted theoretically for freestanding silicene, allowing the conclusion that its prominent electronic properties are preserved. The absorption features are, however, modified by many-body effects induced by the Au substrate due to an increased screening of electron-hole interactions.Unprecedented copper-catalyzed regiodivergent hydrosilylation reactions of substituted 1,3-dienes with hydrosilanes have been developed. The 1,2- and 1,4-hydrosilylations of 1-(hetero)aryl-substituted 1,3-dienes were highly selectively controlled via variation of the catalytic systems. Meanwhile, the 1,4-hydrosilylation reaction of 2-aryl-substituted 1,3-dienes with diphenylsilane was also successfully realized for the first time. These methods provide convenient and efficient approaches for the synthesis of structurally diverse allylsilanes.A protecting-group-free synthesis of two endoperoxide natural products, plakortolide E and plakortolide I, is reported. Key steps are a vanadium-mediated epoxidation, an iron-catalyzed allylic substitution, and a cobalt-induced endoperoxide formation. Our approach combines chemoselective bond-forming reactions and one-pot operations to forge an overall efficient synthesis.A general system achieving three-component intermolecular carbofunctionalization of alkenes is presented, including carboetherification, carboesterification, carboarylation, and carboamination. The scope of the reaction is presented with respect to the carbon electrophile, the olefin, and the nucleophile. Furthermore, the synthesis of γ-lactams via a carboamination reaction is demonstrated in a telescoped three-step protocol.An asymmetric [3 + 2] cycloaddition of vinyl ethylenecarbonates (VECs) and (E)-3-arylvinyl substituted benzo[d] isothiazole 1,1-dioxides has been developed using the Pd complex of a bidentate phosphoramidite (Me-BIPAM) as the catalyst, providing a wide variety of chiral multistereogenic vinyltetrahydrofurans in good yields with excellent diastereo- and enantioselectivities (up to >201 dr, 99% ee).Mannitol, leucine, and trehalose have been widely used in spray-dried formulations, especially for inhalation formulations. The individual contribution of these excipients on protein physical stability in spray-dried solids was studied here using bovine serum albumin (BSA) as a model protein. The spray-dried solids were characterized with scanning electron microscopy, powder X-ray diffraction, and solid-state Fourier-transform infrared spectroscopy to analyze particle morphology, crystallinity, and secondary structure change, respectively. Advanced solid-state characterizations were conducted with solid-state hydrogen-deuterium exchange (ssHDX) and solid-state nuclear magnetic resonance (ssNMR) to explore protein conformation and molecular interactions in the context of the system physical stability. Trehalose remained amorphous after spray-drying and was miscible with BSA, forming hydrogen bonds to maintain protein conformation, whereby this system showed the least monomer loss in the stability study. As indicated by ssNMR, both crystalline and amorphous forms of mannitol existed in the spray-dried BSA-mannitol solids, which explained its partial stabilizing effect on BSA. Leucine showed the strongest crystallization tendency after spray-drying and did not provide a stabilizing effect due to substantial immiscibility and phase separation with BSA as a result of crystal formation. This work showed novel applications of ssNMR in examining protein conformation and protein-excipient interaction in dry formulations. Overall, our results demonstrate the pivotal role of advanced solid-state characterization techniques in understanding the physical stability of spray-dried protein solids.The fundamental understanding of sodium storage mechanisms in amorphous carbon is essential to develop high-performance anode materials for sodium-ion batteries. However, the intrinsic relation between the structure of amorphous carbon and Na+ storage remains to be debated due to the difficulty in controlling and characterizing the local atomic configurations of amorphous carbon. Here we report quantitative measurements of Na+ storage in a low-temperature dealloyed hard carbon with a tunable local structure from completely disordered micropores to gradually increased graphitic order domains. The structure-capacity-potential correlation not only verifies the disputing "adsorption-intercalation" mechanisms, i.e., Na+ intercalation into local graphitic domains for the low-voltage plateaus and adsorption in fully disordered carbon for the sloping voltage profiles, but also unveils a new mechanism of Na+ adsorption on defective sites of graphitic carbon in the medium-potential sloping region. The quantitative investigations provide essential insights into the reaction mechanisms of Na+ with amorphous carbon for designing advanced sodium-ion battery anodes.Low-power trapping of nanoscale objects can be achieved by using the enhanced fields near plasmonic nanoantennas. Unfortunately, in this approach the trap site is limited to the position of the plasmonic hotspots and continuous dynamic manipulation is not feasible. Here, we report a low-frequency electrothermoplasmonic tweezer (LFET) that provides low-power, high-stability and continuous dynamic manipulation of a single nanodiamond. LFET harnesses the combined action of the laser illumination of a plasmonic nanopillar antenna array and low-frequency alternating current (ac) electric field to establish an electrohydrodynamic potential capable of the stable trapping and dynamic manipulation of single nanodiamonds. We experimentally demonstrate the fast transport, trapping, and dynamic manipulation of a single nanodiamond using a low-frequency ac field below 5 kHz and low-laser power of 1 mW. This nanotweezer platform for nanodiamond manipulation holds promise for the scalable assembly of single photon sources for quantum information processing and low noise quantum sensors.Realizing a state of matter in two dimensions has repeatedly proven a novel route of discovering new physical phenomena. Van der Waals (vdW) materials have been at the center of these now extensive research activities. They offer a natural way of producing a monolayer of matter simply by mechanical exfoliation. This work demonstrates that the possible multiferroic state with coexisting antiferromagnetic and ferroelectric orders persists down to the bilayer flake of NiI2. By exploiting the optical second-harmonic generation technique, both magnitude and direction of the ferroelectric order, arising from the cycloidal spin order, are successfully traced. The possible multiferroic state's transition temperature decreases from 58 K for the bulk to about 20 K for the bilayer. Our observation will spur extensive efforts to demonstrate multifunctionality in vdW materials, which have been tried mostly by using heterostructures of singly ferroic ones until now.Despite extensive study, mysteries remain regarding the highly efficient ultrafast charge separation processes in photosynthetic reaction centers (RCs). In this work, transient Stark signals were found to be present in ultrafast two-dimensional electronic spectra recorded for purple bacterial RCs at 77 K. These arose from the electric field that is inherent to the intradimer charge-transfer intermediate of the bacteriochlorophyll pair (P), PA+PB-. By comparing three mutated RCs, a correlation was found between the efficient formation of PA+PB- and a fast charge separation rate. Importantly, the energy level of P* was changed due to the Stark shift, influencing the driving force for P* → P+BA- electron transfer and hence its rate. Furthermore, the orientation and amplitude of the inherent electric field varied in different ways upon different mutation, leading to contrasting changes in the rates. This mechanism of modulation provides a solution to a long-lasting inconsistency between experimental observations and activation energy theory.Halide perovskites make efficient solar cells but suffer from several stability issues. The characterization of these degradation processes is challenging because of the limited spatiotemporal resolution in experiments and the absence of efficient computational methods to study these reactive processes. Here, we present the first reactive force field for molecular dynamics simulations of the phase instability and the defect-induced degradation in CsPbI3. We find that the phase transitions are driven by the anharmonic fluctuations of the atoms in the perovskite lattice. At low temperatures, the Cs cations tend to move away from their preferential positions, resulting in worse contacts with the surrounding metal halide framework which initiates the conversion to a nonperovskite phase. link2 Moreover, our simulations of defective structures reveal that, although both iodine vacancies and interstitials are mobile in the perovskite lattice, the vacancies have a detrimental effect on the stability, leading to the decomposition of perovskites to PbI2.Molecular motors that exhibit controlled unidirectional rotation provide great prospects for many types of applications, including nanorobotics. link3 Existing rotational motors have two key components photoisomerization around a π-bond followed by a thermally activated helical inversion, the latter being the rate-determining step. We propose an alternative molecular system in which the rotation is caused by the electric coupling of chromophores. This is used to engineer the excited state energy surface and achieve unidirectional rotation using light as the only input and avoid the slow thermally activated step, potentially leading to much faster operational speeds. To test the working principle, we employ quantum-classical calculations to study the dynamics of such a system. We estimate that motors built on this principle should be able to work on a subnanosecond time scale for such a full rotation. We explore the parameter space of our model to guide the design of a molecule that can act as such a motor.
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