Facile Construction of Novel 3‑Dimensional Graphene/Amorphous Porous Carbon Hybrids with Enhanced Lithium Storage Properties

Presently, porous materials have become essential to many technological applications. In this account, 3-dimensional skeleton composite materials consisting of a core–shell amorphous porous carbon/multilayer graphene are synthesized by chemical vapor deposition on Ni foam using a facile one-step growth method. The data suggest that these composites have not only outstanding electrical and mechanical properties of the multilayer graphene but also the mesoporous characteristics of the amorphous carbon. Moreover, the composited carbon materials perfectly inherit the macroporous structure of Ni foam, and the amorphous carbon core in the skeleton serves as a cushion to buffer the volume variation after the removal of Ni. The carbon composites reveal ultralow density (4.45 mg cm^–3) and high conductivity (45 S cm^–1), essentially issued from the perfectly preserved structural integrity of graphene. The novel carbon composites can be used as anodes for lithium ion batteries. After these carbon composites are incorporated with NaBiO₃, superior electrochemical activities above 2 V can be achieved with a discharge capacity of ∼300 mAh g^–1

Few-Layer Antimonene: Anisotropic Expansion and Reversible Crystalline-Phase Evolution Enable Large-Capacity and Long-Life Na-Ion Batteries

Two-dimensional (2D) antimonene is a promising anode material in sodium-ion batteries (SIBs) because of its high theoretical capacity of 660 mAh g^–1 and enlarged surface active sites. However, its Na storage properties and sodiation/desodiation mechanism have not been fully explored. Herein, we propose the sodiation/desodiation reaction mechanism of 2D few-layer antimonene (FLA) based on results acquired by <i>in situ</i> synchrotron X-ray diffraction, <i>ex situ</i> selected-area electron diffraction, and theoretical simulations. Our study shows that the FLA undergoes anisotropic volume expansion along the <i>a</i>/<i>b</i> plane and exhibits reversible crystalline phase evolution (Sb ⇋ NaSb ⇋ Na₃Sb) during cycling. Density-functional theory calculations demonstrate that the FLA has a small Na-ion diffusion barrier of 0.14 eV. The FLA delivers a larger capacity of 642 mAh g^–1 at 0.1 C (1 C = 660 mA g^–1) and a high rate capability of 429 mAh g^–1 at 5 C and maintains a stable capacity of 620 mA g^–1 at 0.5 C with 99.7% capacity retention from the 10th to the 150th cycle. Considering the 660 mAh g^–1 theoretical capacity of Sb, the electrochemical utilization of Sb atoms of FLA is as high as 93.9% at a rate of 0.5 C for over 150 cycles, which is the highest capacity and Sb utilization ratio reported so far. Our study discloses the Na storage mechanism of 2D FLA, boosting promising applications of 2D materials for advanced SIBs

Phase 1 Study in Malaria Naïve Adults of BSAM2/Alhydrogel®+CPG 7909, a Blood Stage Vaccine against <em>P. falciparum</em> Malaria

<div><p>A Phase 1 dose escalating study was conducted in malaria naïve adults to assess the safety, reactogenicity, and immunogenicity of the blood stage malaria vaccine BSAM2/Alhydrogel®+ CPG 7909. BSAM2 is a combination of the FVO and 3D7 alleles of recombinant AMA1 and MSP1₄₂, with equal amounts by weight of each of the four proteins mixed, bound to Alhydrogel®, and administered with the adjuvant CPG 7909. Thirty (30) volunteers were enrolled in two dose groups, with 15 volunteers receiving up to three doses of 40 µg total protein at Days 0, 56, and 180, and 15 volunteers receiving up to three doses of 160 µg protein on the same schedule. Most related adverse events were mild or moderate, but 4 volunteers experienced severe systemic reactions and two were withdrawn from vaccinations due to adverse events. Geometric mean antibody levels after two vaccinations with the high dose formulation were 136 µg/ml for AMA1 and 78 µg/ml for MSP1₄₂. Antibody responses were not significantly different in the high dose versus low dose groups and did not further increase after third vaccination. <em>In vitro</em> growth inhibition was demonstrated and was closely correlated with anti-AMA1 antibody responses. A Phase 1b trial in malaria-exposed adults is being conducted.</p> <h3>Trial Registration</h3><p>Clinicaltrials.gov <a href="http://clinicaltrials.gov/ct2/show/NCT00889616">NCT00889616</a></p> </div

<i>In Situ</i> Observation of Thermal Proton Transport through Graphene Layers

Protons can penetrate through single-layer graphene, but thicker graphene layers (more than 2 layers), which possess more compact electron density, are thought to be unfavorable for penetration by protons at room temperature and elevated temperatures. In this work, we developed an <i>in situ</i> subsecond time-resolved grazing-incidence X-ray diffraction technique, which fully realizes the real-time observation of the thermal proton interaction with the graphene layers at high temperature. By following the evolution of interlayer structure during the protonation process, we demonstrated that thermal protons can transport through multilayer graphene (more than 8 layers) on nickel foil at 900 °C. In comparison, under the same conditions, the multilayer graphenes are impermeable to argon, nitrogen, helium, and their derived ions. Complementary <i>in situ</i> transport measurements simultaneously verify the penetration phenomenon at high temperature. Moreover, the direct transport of protons through graphene is regarded as the dominant contribution to the penetration phenomenon. The thermal activation, weak interlayer interaction between layers, and the affinity of the nickel catalyst may all contribute to the proton transport. We believe that this method could become one of the established approaches for the characterization of the ions intercalated with 2D materials <i>in situ</i> and in real-time

Antibody responses shown are the arithmetic mean of the FVO and 3D7 responses for each antigen for all volunteers who received all 3 vaccines and were not excluded per protocol (n = 23).

<p>Thicker lines show the geometric mean response; arrows indicate vaccinations. Mann-Whitney tests with Hodges-Lehmann confidence intervals were done to compare responses in low versus high dose groups and 2 weeks after 2^nd and 3^rd vaccinations (days 70 and 194); although the 160 µg group had slightly higher geometric means (AMA1 D70: Fold Change = 1.49 [95% CI 0.78, 2.92] p = 0.28; AMA1 D194: FC = 1.30 [0.68, 2.49] p = 0.61;MSP1 D70: FC = 1.18 [0.57,2.49] p = 0.70; MSP1 D 194: FC = 1.30 [0.85, 1.91]) p = 0.21; differences were not significant at the 0.05 level.</p

Participants flow sheet.

<p>Thirty (30) participants were enrolled, 24 participants completed vaccinations, and 24 completed follow-up to Day 360.</p

Characterization of MSP1₄₂-FUP-EPA conjugates.

<p>Panel (A) Coomassie blue stained SDS-PAGE gel analysis of maleimide-EPA (lanes 1 and 5); monomeric MSP1₄₂-FUP (lanes 2 and 6), un-purified conjugation mixture of MSP1₄₂-FUP-EPA_APA (lane 3), bulk purified MSP1₄₂-FUP-EPA_APA (lane 4); un-purified conjugation mixture of MSP1₄₂-FUP-EPA_PEO (lane 7) and bulk purified MSP1₄₂-FUP-EPA_PEO (lane 8). The asterisks indicate the conjugates with 3∶1 and 4∶1 ratio. Panel (B) SEC-HPLC-MALS analysis. Solid and dashed lines represent absorbance at 280 nm and molecular mass for MSP1₄₂-FUP-EPA_PEO and MSP1₄₂-FUP-EPA_APA, respectively. The capital letters A, B and C indicate the profile peaks of each conjugate.</p

Local (injection site pain, tenderness, erythema, swelling, induration) and related systemic adverse events after first, second and third vaccinations in the high dose group.

<p>The x-axis shows the number of participants experiencing adverse events, with the highest severity event for each participant after each vaccination shown. Other systemic adverse events in both high and low dose groups were: diarrhea (1 severe, 2 mild), abdominal pain, nausea, and cough (all mild or moderate).</p

In vitro growth inhibition of homologous 3D7 parasites as a function of specific antibody concentration is shown.

<p>Purified IgG from Day 70 samples (two weeks after the second vaccination) were used at a concentration of 10 mg/mL.</p

Correlation between average anti-AMA1 and -MSP1₄₂ antibody responses at Day 70 and Day 194 (two weeks after second and third vaccinations).

<p>Day 70: Spearman correlation, r = 0.60 [95% CI 0.23, 0.82]; Day 194: Spearman's correlation, r = 0.75 [0.50,0.89].</p