Operando Optical Imaging of Cathode Swelling Process Inside Lithium Primary Batteries: Comparative Studies between Different Structured CF.

As a crucial cathode material with ultrahigh theoretical capacity (865 mAh/g) and energy density (>2100 Wh/kg), fluorinated carbon (CF) is promising for lithium primary batteries. However, the operating performance of CF cathode is hindered by nonuniform volume expansion during discharging. To investigate this, we used operando confocal microscopy to visualize the thickness evolution of two different CF cathodes and quantified their swelling ratios as a function of the discharge depth.

Fluorinated aggregated nanocarbon with high discharge voltage as cathode materials for alkali-metal primary batteries.

Due to its exceptionally high theoretical energy density, fluorinated carbon has been recognized as a strong contender for the cathode material in lithium primary batteries particularly valued in aerospace and related industries. However, CF cathode with high F/C ratio, which enables higher energy density, often suffer from inadequate rate capability and are unable to satisfy escalating demand. Furthermore, their intrinsic low discharge voltage imposes constraints on their applicability.

Protecting Li-metal anode with LiF-enriched solid electrolyte interphase derived from a fluorinated graphene additive.

As the holy-grail material, the Li-metal anode has been considered the potential anode of the next generation of Li-metal batteries (LMBs). However, issues of undesirable dendrite growth and unsatisfactory reversibility of the Li-plating/stripping process during the electrochemical cycling impede further application of LMBs. Herein, we innovatively introduce fluorinated graphene (F-Gr) species as a sacrificial effective electrolyte additive into EC/EMC-based electrolyte, which effectively triggers LiF-enriched (composition) and organic/inorganic species uniform-distributed (structure) SEI film architecture that features robustness and denseness, as well as good stability.

Boosting the Electrochemical Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes.

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, MnFeF@CF was generated by the all-fluoride strategy, converting most of the carbon in MnFeF@C into electrochemical active CF through a controllable NF gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite.

In-situ texturing hollow carbon host anchored with Fe single atoms accelerating solid-phase redox for Li-Se batteries.

Se-based cathodes have caught tremendous attention owing to their comparable volumetric capacity and better electronic conductivity to S cathodes. However, its low utilization ratio and sluggish redox kinetics due to the high reaction barrier of solid-phase transformation from Se to LiSe limit its practical application. Herein, an in-situ texturing hollow carbon host by gas-solid interface reaction anchored with Fe single-atomic catalyst is designed and prepared for advanced Li-Se batteries.

Fluorinated carbon as high-performance cathode for aqueous zinc primary batteries.

Fluorinated carbon (CF) has been extensively served as promising positive electrode material for lithium primary batteries due to its high energy density. However, there are comparatively far less reports about the use of CF on other battery systems, let alone on the research of aqueous batteries. Herein in this study, we employed CF as the cathode active for aqueous zinc batteries for the first time and systematically investigated its electrochemical behavior under a series of aqueous zinc-ion electrolytes.

Stabilizing Li-O Batteries with Multifunctional Fluorinated Graphene.

As a full cell system with attractive theoretical energy density, challenges faced by Li-O batteries (LOBs) are not only the deficient actual capacity and superoxide-derived parasitic reactions on the cathode side but also the stability of Li-metal anode. To solve simultaneously intrinsic issues, multifunctional fluorinated graphene (CF, = 1, F-Gr) was introduced into the ether-based electrolyte of LOBs. F-Gr can accelerate O transformation and O-participated oxygen reduction reaction (ORR) process, resulting in enhanced discharge capacity and restrained O-derived side reactions of LOBs, respectively.

High-Power-Density, High-Energy-Density Fluorinated Graphene for Primary Lithium Batteries.

Li/CF is one of the highest-energy-density primary batteries; however, poor rate capability hinders its practical applications in high-power devices. Here we report a preparation of fluorinated graphene (GF) with superior performance through a direct gas fluorination method. We find that the so-called "semi-ionic" C-F bond content in all C-F bonds presents a more critical impact on rate performance of the GF in comparison with sp C content in the GF, morphology, structure, and specific surface area of the materials.

Single-Molecule Observation Reveals Spontaneous Protein Dynamics in the Nucleosome.

Structural dynamics of a protein molecule is often critical to its function. Single-molecule methods provide efficient ways to investigate protein dynamics, although it is very challenging to achieve a millisecond or higher temporal resolution. Here we report spontaneous structural dynamics of the histone protein core in the nucleosome based on a single-molecule method that can reveal submillisecond dynamics by combining maximum likelihood estimation and fluorescence correlation spectroscopy.

Single-Molecule Studies of the Linker Histone H1 Binding to DNA and the Nucleosome.

Linker histone H1 regulates chromatin structure and gene expression. Investigating the dynamics and stoichiometry of binding of H1 to DNA and the nucleosome is crucial to elucidating its functions. Because of the abundant positive charges and the strong self-affinity of H1, quantitative in vitro studies of its binding to DNA and the nucleosome have generated results that vary widely and, therefore, should be interpreted in a system specific manner.

Dynamics of nucleosome assembly and effects of DNA methylation.

The nucleosome is the fundamental packing unit of the eukaryotic genome, and CpG methylation is an epigenetic modification associated with gene repression and silencing. We investigated nucleosome assembly mediated by histone chaperone Nap1 and the effects of CpG methylation based on three-color single molecule FRET measurements, which enabled direct monitoring of histone binding in the context of DNA wrapping. According to our observation, (H3-H4)2 tetramer incorporation must precede H2A-H2B dimer binding, which is independent of DNA termini wrapping.

Dark-field illumination on zero-mode waveguide/microfluidic hybrid chip reveals T4 replisomal protein interactions.

The ability of zero-mode waveguides (ZMWs) to guide light energy into subwavelength-diameter cylindrical nanoapertures has been exploited for single-molecule fluorescence studies of biomolecules at micromolar concentrations, the typical dissociation constants for biomolecular interactions. Although epi-fluorescence microscopy is now adopted for ZMW-based imaging as an alternative to the commercialized ZMW imaging platform, its suitability and performance awaits rigorous examination. Here, we present conical lens-based dark-field fluorescence microscopy in combination with a ZMW/microfluidic chip for single-molecule fluorescence imaging.

Synthesis and characterization of fluorinated carbon nanotubes for lithium primary batteries with high power density.

The synthesis and characterization of fluorinated carbon nanotubes have been carried out under an inert gas containing fluorine. All of the samples have been characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance ((13)C and (19)F ss-NMR) and transmission electron microscopy (TEM) techniques. The comparison of the effects of various experimental parameters on the structure of fluorinated materials allows the disclosure of the fluorination mechanism.

Insights into Okazaki fragment synthesis by the T4 replisome: the fate of lagging-strand holoenzyme components and their influence on Okazaki fragment size.

In this study, we employed a circular replication substrate with a low priming site frequency (1 site/1.1 kb) to quantitatively examine the size distribution and formation pattern of Okazaki fragments. Replication reactions by the T4 replisome on this substrate yielded a patterned series of Okazaki fragments whose size distribution shifted through collision and signaling mechanisms as the gp44/62 clamp loader levels changed but was insensitive to changes in the gp43 polymerase concentration, as expected for a processive, recycled lagging-strand polymerase.

Lab-on-a-chip technologies for single-molecule studies.

Recent developments on various lab-on-a-chip techniques allow miniaturized and integrated devices to perform on-chip single-molecule studies. Fluidic-based platforms that utilize unique microscale fluidic behavior are capable of conducting single-molecule experiments with high sensitivities and throughputs, while biomolecular systems can be studied on-chip using techniques such as DNA curtains, magnetic tweezers, and solid-state nanopores. The advances of these on-chip single-molecule techniques lead to next-generation lab-on-a-chip devices, such as DNA transistors, and single-molecule real-time (SMRT) technology for rapid and low-cost whole genome DNA sequencing.

The human lagging strand DNA polymerase δ holoenzyme is distributive.

Polymerase δ is widely accepted as the lagging strand replicative DNA polymerase in eukaryotic cells. It forms a replication complex in the presence of replication factor C and proliferating cell nuclear antigen to perform efficient DNA synthesis in vivo. In this study, the human lagging strand holoenzyme was reconstituted in vitro.

On-chip manipulation of single microparticles, cells, and organisms using surface acoustic waves.

Techniques that can dexterously manipulate single particles, cells, and organisms are invaluable for many applications in biology, chemistry, engineering, and physics. Here, we demonstrate standing surface acoustic wave based "acoustic tweezers" that can trap and manipulate single microparticles, cells, and entire organisms (i.e.

Single-molecule studies of DNA replisome function.

Fast and accurate replication of DNA is accomplished by the interactions of multiple proteins in the dynamic DNA replisome. The DNA replisome effectively coordinates the leading and lagging strand synthesis of DNA. These complex, yet elegantly organized, molecular machines have been studied extensively by kinetic and structural methods to provide an in-depth understanding of the mechanism of DNA replication.

Evolution in the supramolecular complexes between poly(phenylene ethynylene)-based polyelectrolytes and octadecyltrimethylammonium bromide as revealed by fluorescence correlation spectroscopy.

Poly(phenyleneethynylene)-based conjugated polyelectrolytes (PPE-SO(3)(-)) are a class of polyions with rigid backbones. This work uses fluorescence correlation spectroscopy to study how the diffusion of complexes, formed between a PPE-SO(3)(-) polyelectrolyte and octadecyltrimethylammonium bromide (OTAB) surfactant molecules, changes with OTAB concentration below its critical micelle concentration. The dependence of the hydrodynamic radius of the complexes on the OTAB concentration has three regimes.

Controllable synthesis of α- and β-MnO(2): cationic effect on hydrothermal crystallization.

α- and β-MnO(2) were controllably synthesized by hydrothermally treating amorphous MnO(2) obtained via a reaction between Mn(2+) and MnO(4)(-), and cationic effects on the hydrothermal crystallization of MnO(2) were investigated systematically. The crystallization is believed to proceed by a dissolution-recrystallization mechanism; i.e.

Charge density effects on the aggregation properties of poly(p-phenylene-ethynylene)-based anionic polyelectrolytes.

This work shows that low charge density poly(p-phenylene-ethynylene)s (PPE-SO3Na-L and PPE-CO2Na-L), which feature sulfonate and carboxylate groups on every other phenyl ring, form aggregates in water, whereas high charge density poly(p-phenylene-ethynylene)s (PPE-SO3Na-H and PPE-CO2Na-H), which possess sulfonate or carboxylate groups on every phenyl ring, do not aggregate in water. The formation of aggregates of PPE-SO3Na-L and PPE-CO2Na-L is demonstrated by comparing the concentration and temperature dependence of their steady-state spectra in water to that in DMSO, in which the two polymers do not aggregate. For the weak polyelectrolytes PPE-CO2Na-H and PPE-CO2Na-L, the solution pH was changed to vary the charge density.

Solvation and aggregation of polyphenylethynylene based anionic polyelectrolytes in dilute solutions.

The absorption and fluorescence properties of a polyphenylethynylene based conjugated polyelectrolyte with sulfonate solubilizing groups (PP2) are shown to change dramatically with solution conditions because of the equilibrium between unaggregated and aggregated forms of the polymer. The fluorescence of PP2 is strongly quenched on addition of counterions such as Na+, K+, Li+, and TBA+, an effect which arises from the creation of salt stabilized aggregates. The formation of aggregates has been further corroborated by concentration and temperature studies in water and comparisons to dimethylsulfoxide solvent, in which the polymer does not aggregate.

On the electron transfer mechanism between cytochrome C and metal electrodes. Evidence for dynamic control at short distances.

Cytochrome c was coordinatively bound to self-assembled monolayers of pyridine-terminated alkanethiols on Au and Ag electrodes. The mechanism of heterogeneous electron transfer of the immobilized protein was investigated by cyclic voltammetry and time-resolved surface-enhanced resonance Raman spectroelectrochemistry. The temperature, distance, and overpotential dependencies of the electron transfer rates indicate a change of mechanism from a tunneling controlled reaction at long distances (thicker films) to a solvent/protein friction controlled reaction at smaller distances (thinner films).

The effect of ionic strength on the electron-transfer rate of surface immobilized cytochrome C.

Horse heart cytochrome c was immobilized on four different self-assembled monolayer (SAM) films. The electron tunneling kinetics were studied in the different assemblies as a function of the ionic strength of the buffer solution using cyclic voltammetry. When cytochrome c is electrostatically immobilized, the standard electron exchange rate constant k0 decreases with the increase of the solution's ionic strength.

Impact of surface immobilization and solution ionic strength on the formal potential of immobilized cytochrome C.

Four different self-assembled monolayer (SAM) electrode systems were examined electrochemically in order to better understand surface charge effects on the redox thermodynamics of immobilized horse heart cytochrome c (cyt c). Neutralization of protein surface charge upon adsorption on anionic COOH-terminated SAMs was found to cause substantial changes in the formal potential, as determined by cyclic voltammetry. For cyt c immobilized on negatively charged surfaces, the formal potential shifted to more negative values as the ionic strength was decreased, which is opposite to the trend displayed by solution cyt c.