Charged Aggregates Research Articles

Transitioning from Regular Electrolytes to Solvate Ionic Liquids to High-Concentration Electrolytes: Changes in Transport Properties and Ionic Speciation.

Glyme-based lithium-ion electrolytes have received considerable attention from the scientific community due to their improved safety, as well as electrochemical and thermal stability over carbonate-based electrolytes. However, these electrolytes suffer from major drawbacks such as high viscosities. To overcome the challenges that hinder their full potential, the molecular description of glyme-based lithium electrolytes in the high-concentration regime, particularly in the solvate ionic liquid (SIL) and high-concentration electrolyte (HCE) regimes, is needed. In this study, model glyme-based electrolytes based on a lithium thiocyanate and either tetraglyme (G4) or a mixture of monoglyme (G1) and diglyme (G2) were investigated as a function of the solvent-to-lithium ratio using linear and nonlinear IR spectroscopies, in combination with ab initio computations as well as electrochemical methods . The transport properties reveal enhanced ionicities in the HCE and SIL regimes ([O]/[Li] ≤ 5) compared to the regular electrolytes (REs, with [O]/[Li] > 5) in both pure (G4) and mixed (G1:G2) glymes. IR and ab initio computations relate these larger ionicities to the higher concentration of charged aggregates in the HCE and SIL electrolytes ([O]/[Li] ≤ 5). Moreover, it was observed that the use of mixed glymes appears to have a minimal effect on the transport properties of REs but exhibits deleterious effects on SILs. Overall, the results provide a molecular framework for describing the local structure of lithium glyme-based electrolytes and demonstrate the key role that the nature of glyme solvation plays in the molecular structure and consequently the macroscopic properties of the Li-glyme SILs, HCEs, and REs.

Observation of Large, Charged Droplet Signatures within the High-Vacuum Region of a Commercial Electrospray TOF-MS.

Electrospray ionization (ESI) is one of the most prominent atmospheric pressure ionization techniques in modern mass spectrometry. It generates charged droplets from an analyte-containing solution as an initial step in the ionization process. Textbooks and the majority of the articles assume the entire droplet evaporation and release of bare analyte ions within the ionization chamber. However, non-mass-spectrometry-related literature and recent reports demonstrate droplet observation in regions of the vacuum systems of a variety of mass spectrometers. In this work, we report on the observation of large droplet fragments within the orthogonal acceleration stage of a Bruker micrOTOF by connecting an oscilloscope to an auxiliary ion current detector downstream of the acceleration stage. Moreover, we detected fragment debris even with the MCP TOF detector by evaluating individual TOF spectra. Droplet fragments appear as pronounced and intensive pulses of the ion current. This observation is clearly connected to ESI, as other atmospheric pressure ionization methods do not show this behavior. The recorded droplet signatures show clear dependencies on the ion source and transfer stage parameters. The existence of large and highly charged droplets may adversely affect or at least impact the analytical performance of the instrument due to space charge or complex heterogeneous chemical reactions. Furthermore, the penetration of large charged aggregates into the vacuum system explains the reported surface contamination after multipole stages. This contamination of critical components leads to substantially higher maintenance efforts.

Electric field induced associations in the double layer of salt-in-ionic-liquid electrolytes.

Ionic liquids (ILs) are an extremely exciting class of electrolytes for energy storage applications. Upon dissolving alkali metal salts, such as Li or Na based salts, with the same anion as the IL, an intrinsically asymmetric electrolyte can be created for use in batteries, known as a salt-in-ionic liquid (SiIL). These SiILs have been well studied in the bulk, where negative transference numbers of the alkali metal cation have been observed from the formation of small, negatively charged clusters. The properties of these SiILs at electrified interfaces, however, have received little to no attention. Here, we develop a theory for the electrical double layer (EDL) of SiILs where we consistently account for the thermoreversible association of ions into Cayley tree aggregates. The theory predicts that the IL cations first populate the EDL at negative voltages, as they are not strongly bound to the anions. However, at large negative voltages, which are strong enough to break the alkali metal cation-anion associations, these IL cations are exchanged for the alkali metal cation because of their higher charge density. At positive voltages, we find that the SiIL actually becomes more aggregated while screening the electrode charge from the formation of large, negatively charged aggregates. Therefore, in contrast to conventional intuition of associations in the EDL, SiILs appear to become more associated in certain electric fields. We present these theoretical predictions to be verified by molecular dynamics simulations and experimental measurements.

Peptide Amphiphiles as Biodegradable Adjuvants for Efficient Retroviral Gene Delivery.

Retroviral gene delivery is the key technique for in vitro and ex vivo gene therapy. However, inefficient virion-cell attachment resulting in low gene transduction efficacy remains a major challenge in clinical applications. Adjuvants for ex vivo therapy settings need to increase transduction efficiency while being easily removed or degraded post-transduction to prevent the risk of venous embolism after infusing the transduced cells back to the bloodstream of patients, yet no such peptide system have been reported thus far. In this study, peptide amphiphiles (PAs) with a hydrophobic fatty acid and a hydrophilic peptide moiety that reveal enhanced viral transduction efficiency are introduced. The PAs form β-sheet-rich fibrils that assemble into positively charged aggregates, promoting virus adhesion to the cell membrane. The block-type amphiphilic sequence arrangement in the PAs ensures efficient cell-virus interaction and biodegradability. Good biodegradability is observed for fibrils forming small aggregates and it isshown that via molecular dynamics simulations, the fibril-fibril interactions of PAs are governed by fibril surface hydrophobicity. These findings establish PAs as additives in retroviral gene transfer, rivalling commercially available transduction enhancers in efficiency and degradability with promising translational options in clinical gene therapy applications.

Drug Aggregation of Sparingly-Soluble Ionizable Drugs: Molecular Dynamics Simulations of Papaverine and Prostaglandin F2α.

Aggregation in aqueous solution can have important implications on both the in vivo exposure of a drug and its pharmaceutical manufacturability. However, the drug aggregates formed can be very small and, thus, difficult to interrogate experimentally. On the other hand, at higher supersaturations where larger aggregates are supported, the chemical system is inherently metastable and therefore likewise challenging to study from an experimental standpoint. Understanding aggregation behavior is further complicated in the case of ionizable drugs where, unlike neutral compounds, there can be uncertainty in the kinds of drug molecules (i.e., charged, neutral, or both) that become incorporated into various clusters, particularly at pH values near the pKa. In this paper, we apply physics-based all-atom molecular dynamics (MD) simulations to study aggregation in the weakly basic drug papaverine and in the weakly acidic drug prostaglandin F2α. We employ in silico tools to construct simulation workflows and comprehensive cluster analysis protocols to elucidate the size distributions and dynamics of the drug aggregates formed at both an experimentally relevant concentration and at high supersaturation. We build on a previously published treatment [Solubility of sparingly soluble ionizable drugs. Adv. Drug Deliv. Rev. 2007, 59, 568-590, DOI: 10.1016/j.addr.2007.05.008] to translate the predicted aggregate distributions of each ionized drug into corresponding pH-solubility curves that can be compared directly to experiment. Our findings show that the assumption of a single predominant (charged) aggregate can be misleading in interpreting experimental pH-solubility curves, as it does not adequately reflect the rich diversity revealed in our simulations. Beyond not accounting for the distribution of ionized drug-containing clusters actually observed in solution, for both drugs we find evidence that neutral drug molecules can also participate in the aggregation phenomena. Notably, we observe that many drug molecules remain as free monomers in solution even under simulated conditions designed to mimic those where there is significant deviation of the experimental pH-solubility curve from the Henderson-Hasselbalch (H-H) equation, often taken to be a clear signpost of drug aggregation.

Computational modeling of the effect of skin pinch and stretch on subcutaneous injection of monoclonal antibodies using autoinjector devices.

Subcutaneous injection of monoclonal antibodies (mAbs) has experienced unprecedented growth in the pharmaceutical industry due to its benefits in patient compliance and cost-effectiveness. However, the impact of different injection techniques and autoinjector devices on the drug's transport and uptake is poorly understood. Here, we develop a biphasic large-deformation chemomechanical model that accounts for the components of the extracellular matrix that govern solid deformation and fluid flow within the subcutaneous tissue: interstitial fluid, collagen fibers and negatively charged proteoglycan aggregates. We use this model to build a high-fidelity representation of a virtual patient performing a subcutaneous injection of mAbs. We analyze the impact of the pinch and stretch methods on the injection dynamics and the use of different handheld autoinjector devices. The results suggest that autoinjector base plates with a larger device-skin contact area cause significantly lower tissue mechanical stress, fluid pressure and fluid velocity during the injection process. Our simulations indicate that the stretch technique presents a higher risk of intramuscular injection for autoinjectors with a relatively long needle insertion depth.

Nucleation by a charged particle in fluids containing salt

We present a model to describe ion-induced nucleation in fluids. Nucleation is induced by a charged molecular aggregate, a large ion, a charged colloid, or an aerosol particle. This model generalizes the Thomson model to polar environments. Solving the Poisson-Boltzmann equation, we find the potential profiles around the charged core and calculate the energy. Our results are analytical in the Debye-Hückel limit and numerical otherwise. From the Gibbs free energy curve vs. nucleus size, we find the metastable and stable states and the energy barrier between them, for varying saturation values, core's charge, and amount of salt. The nucleation barrier decreases with increasing core charge or Debye length. We calculate the phase lines in the phase diagram of supersaturation and core charge. We find regions of one phase, electro-prewetting, spontaneous nucleation, ion-induced nucleation, and classical-like nucleation.

Charged Atmospheric Aerosols from Charged Saltating Dust Aggregates

Grain collisions in aeolian events, e.g., due to saltation, result in atmospheric aerosols. They may regularly be electrically charged, but individual charge balances in collisions including small grains are not easily obtained on the ground. We therefore approach this problem in terms of microgravity, which allows for the observation of collisions and the determination of small charges. In a drop tower experiment, ∼1 mm dust aggregates are traced before and after a collision within the electric field of a plate capacitor. The sum of the electric charge of two particles (total charge) before and after the collision often strongly deviates from charge conservation. Due to the average low collision velocities of 0.2 m/s, there is no large scale fragmentation. However, we do observe small charged particles emerging from collisions. The smallest of these particles are as small as the current resolution limit of the optical system, i.e., they are at least as small as tens of µm. In the given setting, these small fragments may carry 1 nC/m2–1 µC/m2 which is between 1% and ten times the surface charge density of the large aggregates. These first experiments indicate that collisions of charged aggregates regularly shed charged grains into the atmosphere, likely down to the suspendable aerosol size.

Dual-Mechanism Glycolipidpeptide with High Antimicrobial Activity, Immunomodulatory Activity, and Potential Application for Combined Antibacterial Therapy.

Bacterial drug resistance is becoming increasingly serious, and it is urgent to develop effective antibacterial drugs. Antimicrobial peptides (AMPs), as potential candidates against bacteria, have a broad prospect for development. Herein, a series of AMPs with biological characteristics (net positive charge, amphiphilicity, and α-helix), an AXA motif recognized by membrane bound serine protease type I signal peptidases (SPase I), an FLPII motif to reduce hemolysis, and a monosaccharide motif to improve the stability and activity were designed and synthesized, and among which, the glycolipidpeptide GLP6 (glycosylated LP6 lipopeptide) had excellent antibacterial and immunomodulatory activity, good stability and biocompatibility, and excellent biofilm eradication and membrane penetrating activity. The positively charged spherical aggregates formed by self-assembly of GLP6 could encapsulate tetracycline (TC) to form GLP6@TC with a sustained-release effect, which could enhance the sensitivity of bacteria to the antibiotic and realize combined sterilization. The results of acute peritonitis and bacterial keratitis showed that GLP6@TC had a good combined antibacterial effect and the ability to inhibit interleukin-2 (IL-2), which could significantly reduce the inflammatory response while treating bacterial infection, and it had great potential for application. The results of computer molecular docking showed the AXA motif could effectively bind to SPase I, which was consistent with the results of biological experiments. In general, the study could provide a perspective for the design of AMPs and combined antibacterial therapy.

Localized Charge on Surfactant-Wrapped Single-Walled Carbon Nanotubes

As-synthesized, semiconducting single-walled carbon nanotubes (SWCNTs) are nominally charge neutral. However, ionic surfactants that are commonly used to disperse SWCNTs in solution can lead to significantly charged aggregates adsorbed to the nanotube. Here, electrostatic force microscopy (EFM) was used to characterize the static-charge interactions between individual SWCNTs and the local environment. We report nonuniform spatial charge distributions with highly varying magnitudes ranging between ±15 e associated with surfactant coverage on long SWCNTs (>1.5 μm). EFM images acquired after resonant photoexcitation demonstrate charge carrier localization due to electrostatic interactions with charged surfactant aggregates. Charge densities as measured by EFM are used to estimate the depth of this electrostatically induced potential well, calculated to be on the order of hundreds of millielectronvolts, suggesting that surfactant charges heterogeneously covering SWCNTs provide traps for excitons potentially leading to their localization.

Tricks for organic-capped Cu2-xS nanoparticles encapsulation into silica nanocomposites co-doped with red emitting luminophore for NIR activated-photothermal/chemodynamic therapy

The present work introduces the factors controlling the encapsulation of oleate-oleylamine-stabilized Cu(2−x)S nanoparticles (NPs) into silica nanocomposites (SNs) through the water-in-oil microemulsion method. The tendency of the Cu(2−x)S NPs to form negatively charged aggregates is highlighted as the factor restricting their loading into the SNs. The different preliminary treating of Cu(2−x)S NPs reveals that the recharging is rather than the de-aggregation facilitates their loading into the SNs. The treating of Cu(2−x)S NPs by [Ru(dipy)3]2+ complexes both facilitates their loading into the SNs and gain in their luminescence. The interfacial post-treating of the SNs by pluronic F-127 (F-127) is represented as the factor affecting both aggregation behavior and therapeutic function of the SNs. The electron spin resonance (ESR) spectroscopy results reveal the factors (heating, treating by F-127, addition of glutathione) that suppress and enhance the generation of reactive oxygen species (ROS) by the SNs. The luminescence of the SNs reveals the specificity in the intracellular trafficking of their treated and untreated counterparts. The cytotoxicity enhancement under the low power NIR-irradiation of the cancer cells incubated by the SNs is explained by the heating-induced increase in the level of ROS generation. The greater cytotoxicity of the treated by F-127 vs the untreated SNs both in “dark” and NIR-irradiated conditions is correlated with the difference in their ability to stand against the suppressive effect of glutathione.

Coassembled Chitosan-Hyaluronic Acid Nanoparticles as a Theranostic Agent Targeting Alzheimer's β-Amyloid.

β-Amyloid (Aβ) fibrillogenesis is closely associated with the pathogenesis of Alzheimer's disease (AD), so detection and inhibition of Aβ aggregation are of significance for the theranostics of AD. In this work, the coassembled nanoparticles of chitosan and hyaluronic acid cross-linked with glutaraldehyde (CHG NPs) were found to work as a theranostic agent for imaging/probing and inhibition of Aβ fibrillization both in vitro and in vivo. The biomass-based CHG NPs of high stability exhibited a wide range of excitation/emission wavelengths and showed binding affinity toward Aβ aggregates, especially for soluble Aβ oligomers. CHG NPs displayed weak emission in the monodispersed state, while they remarkably emitted increased red fluorescence upon interacting with Aβ oligomers and fibrils, showing high sensitivity with a detection limit of 0.1 nM. By comparing the different fluorescence responses of CHG NPs and Thioflavin T to Aβ aggregation, the Aβ oligomerization rate during nucleation can be determined. Moreover, the fluorescence recognition behavior of CHG NPs was selective. CHG NPs specifically bind to negatively charged amyloid aggregates but not to positively charged amyloids and negatively charged soluble proteins. Such enhancement in fluorescence emission is attributed to the clustering-triggered emission effect of CHG NPs after interaction with Aβ aggregates via various electronic conjugations and hydrogen bonding, electrostatic, and hydrophobic interactions. Besides fluorescent imaging/probing, CHG NPs over 360 μg/mL could almost completely inhibit the formation of Aβ fibrils, exhibiting the capability of regulating Aβ aggregation. In-vivo assays with Caenorhabditis elegans CL2006 demonstrated the potency of CHG NPs as an effective theranostic nanoagent for imaging Aβ plaques and inhibiting Aβ deposition. The findings proved the potential of CHG NPs for development as a potent agent for the diagnosis and treatment of AD.

Enhanced Hydrodynamic Radius of AOT/n-heptane/Water Reverse Micellar System Through Altered Electrostatic Interactions and Molecular Self-Assemblies.

We have demonstrated a unique approach to alter the aqueous pool size of an AOT/n-heptane/water reverse micellar system. A positively charged dye Rhodamine B (RhB) and negatively charged Rose Bengal (RB) were incorporated in the reverse micellar pool to investigate the effect of electrostatic interactions and stacking effects among the dye molecules on the AOT/n-heptane/water interface. Dynamic light scattering revealed increase in reverse micellar pool size in presence of positively charged dye aggregates at the oil-water interface. However, less expansion was observed in presence of negatively charged dye aggregates (RB). This confirms the role of electrostatic interaction in modulating the hydrodynamic radius. A head-to-tail type of stacking of RhB molecules at the interface favors this expansion. The differences in stacking of the two dyes inside the reverse micelles and their torsional mobility indicated the role of the reverse micellar interface and H-bonding ability of the microenvironment on dye aggregation. Conductivity measurements demonstrated a significant drop in percolation temperature of the reverse micellar system in presence of dye aggregates. This confirms the effect of dye aggregation and electrostatic interaction on such expansion. This strategy can be exploited for solubilizing greater amounts and a wider variety of drug molecules in microemulsions.

A molecular dynamics study of a fully zwitterionic copolymer/ionic liquid-based electrolyte: Li+ transport mechanisms and ionic interactions.

The development of polymer electrolytes (PEs) is crucial for advancing safe, high-energy density batteries, such as lithium-metal and other beyond lithium-ion chemistries. However, reaching the optimum balance between mechanical stiffness and ionic conductivity is not a straightforward task. Zwitterionic (ZI) gel electrolytes comprising lithium salt and ionic liquid (IL) solutions within a fully ZI polymer network can, in this context, provide useful properties. Although such materials have shown compatibility with lithium metal in batteries, several fundamental structure-dynamic relationships regarding ionic transport and the Li+ coordination environment remain unclear. To better resolve such issues, molecular dynamics simulations were carried out for two IL-based electrolyte systems, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP][TFSI]) with 1M LiTFSI salt and a ZI gel electrolyte containing the IL and a ZI copolymer: poly(2-methacryloyloxyethyl phosphorylcholine-co-sulfobetaine vinylimidazole), poly(MPC-co-SBVI). The addition of ZI polymer decreases the [TFSI]- -[Li]+ interactions and increases the IL ion diffusivities, and consequently, the overall ZI gel ionic conductivity. The structural analyses showed a large preference for lithium-ion interactions with the polymer phosphonate groups, while the [TFSI]- anions interact directly with the sulfonate group and the [BMP]+ cations only display secondary interactions with the polymer. In contrast to previous experimental data on the same system, the simulated transference numbers showed smaller [Li]+ contributions to the overall ionic conductivities, mainly due to negatively charged lithium aggregates and the strong lithium-ion interactions in the systems.

Use of Mixed Langmuir Films of Nanoparticles to Form Metal Oxide Materials with the Optimal Surface Charge.

We aimed to prepare metal oxide materials with the optimal surface charge by preparing mixed films of non-modified metal oxide nanoparticles (NPs) with dissimilar isoelectric points (iep). The purpose of preparing such surfaces was to expand the use of metal oxide materials in environments where the solution pH cannot be changed. Langmuir films of SiO2 (iep: pH 2-3) and TiO2 (iep: pH 5-6.6) NPs were first prepared at air-100 mM NaCl aqueous interfaces. This subphase allowed the formation of stable films of the NPs without the need to modify the NPs with surface-active chemicals, whose presence may detrimentally change the properties of the films. The Langmuir films were then transferred and sintered to silicon wafers and their physical properties were characterized using atomic force microscopy (AFM). The AFM images showed that the films were composed of NP aggregates. The average size of the aggregates decreased, and the uniformity of the aggregate sizes and their inter-aggregate spacing increased with the addition of SiO2 NPs to the film of TiO2 NPs. These changes were explained by an increased electrostatic and steric repulsion between the aggregates formed at the air-100 mM NaCl interface due to the adsorption of negatively charged SiO2 NPs to the slightly positively charged TiO2 aggregates. The force-distance curves measured between a SiO2 probe and the sintered films of SiO2 and/or TiO2 NPs in a 1.0 mM NaCl solution adjusted to pH 4 showed that the magnitude of the repulsive force decreased with an increased number of TiO2 NPs in the film. This force change indicated that the surface charge changed when different types of NPs were mixed. These results indicate that mixing different NP types in a Langmuir film at an air-aqueous interface can help change the physical properties of the transferred film.

Observation of bottom-up formation for charged grain aggregates related to pre-planetary evolution beyond the bouncing barrier

Context. Particles in protoplanetary disks go through a number of phases that are dominated by collisions. In each of these events, grains exchange electrical charge via triboelectric effects. This enhances the stability of particle aggregates. Aims. Dielectric grains are easily charged by collisions. Here, we investigate whether a charge is capable of inducing an aggregation of particles and we consider how collision properties, such as sticking velocities and collisional cross-sections, are altered. Methods. We explored aggregation in microgravity experiments based on the observation of the motion of submillimeter (submm) grains following many collisions. In the process, grains attract each other, collide, stick, and ultimately form small aggregates. Results. We observed a bottom-up formation of irregular aggregates from submm grains. While some of the observed trajectories during the approach of grains reflect the presence of a pure Coulomb potential, the motion is not always in agreement with pure Kepler motion. Higher-order potentials of multipole charge distributions stand as a plausible explanation for this behavior. An immediate consequence of charging is that the particles continue to stick to each other at velocities of ~10 cm s−1, while surface forces of neutral grains are only expected to allow sticking below ~1 mm s−1. No bouncing collision was observed among hundreds of collisions in the given parameter range. Applied to early phases of planet formation, the forming aggregates are therefore the first steps in a new growth phase beyond the traditional bouncing barrier in planet formation.

Formation, Stability, and Coagulation of Fullerene Organosols: C70 in Acetonitrile-Toluene Solutions and Related Systems.

This paper is aimed at better understanding the nature of C70 aggregates in organic solvents. As liquid media, acetonitrile-toluene mixed solvents were chosen. At a high content of CH3CN, e.g., 90 vol %, colloidal particles with a size of ca. 225 ± 10 nm are formed with a negative ζ-potential of -(55 ± 5) mV and are stable over time. The interaction with electrolytes containing single-, double-, and triple-charged cations was examined using dynamic light scattering and UV-visible spectra. Additional experiments were carried out with methanol and benzene instead of acetonitrile and toluene, respectively. For comparison, data were obtained with C60 organosols. It was found that coagulation obeys the classical Schulze-Hardy rule. The specificity of the coagulating power of various single-charged cations was explained by their different abilities to adsorb on negatively charged C70 aggregates. The overcharging effect is expressed not only for Ca2+ and La3+ ions but even for Li+ and is caused by poor solvation of such cations in a cationophobic solvent, acetonitrile. After introduction of the cryptand [2.2.2], a substantial increase in the critical concentrations of coagulation for Na+, Li+, and Ca2+ was observed owing to conversion of "bare" metal cations into their cryptates. The application of the Derjaguin-Landau-Verwey-Overbeek theory allowed for evaluation of the Hamaker constant of the C70-C70 interaction in vacuum, AFF, which lies in the interval of 5.8-16.6 × 10-20 J. Such an estimate, close to that made previously for C60 organosols, was received after withdrawing electrolytic systems where the hetero- and mutual coagulation were highly likely. However, it is impossible to completely exclude the interfering influence of the latter phenomena. Based on the obtained AFF values, two approaches to understanding the behavior of fullerenes in water were proposed.

Group 14 Metallafluorenes as Sensitive Luminescent Probes of Surfactants in Aqueous Solution.

Sila- and germafluorenes containing alkynyl(aryl) substituents at the 2,7- position are strongly emissive with high quantum yields in organic solvents. Provided they are sufficiently soluble in water, their hydrophobic structures have the potential for many biological and industrial applications in the detection and characterization of lipophilic structures. To that end, the emission behaviors of previously synthesized 2,7- bis[alkynyl(biphenyl)]-9,9-diphenylsilafluorene (1), 2,7- bis[alkynyl(methoxynaphthyl)]-9,9-diphenylgermafluorene (2), 2,7- bis[alkynyl(p-tolyl)]-9,9-diphenylsilafluorene (3), and 2,7- bis[alkynyl(m-fluorophenyl)]-9,9-diphenylsilafluorene (4) were characterized in aqueous solution and in the presence of various surfactants. Despite a high degree of hydrophobicity, all of these metallafluorenes (MFs) are soluble in aqueous solution at low micromolar concentrations and luminesce in a common aqueous buffer. Further, the 2,7 substituent makes the emission behavior tunable (up to 30 nm). Fold emission enhancements in the presence of various surfactants are highest toward Triton X-100 and CTAB (ranging from 5 to 25 fold) and are lowest for the anionic surfactants SDS and SDBS. These enhancements are competitive with existing probes of surfactants. Quantum yields in buffer range from 0.11 to 0.34, competitive with many common fluorophores in biological use. Strikingly, MF quantum yields in the presence of TX-100 and CTAB approach 100 % quantum efficiency. MF anisotropies are dramatically increased only in the presence of TX-100, CTAB, and CHAPS. Coupled with the above data, this suggests that MFs associate with neutral and charged surfactant aggregates. Interactions with the anionic surfactants are weaker and/or leave MFs solvent exposed. These properties make metallafluorenes competitive probes for surfactants and their properties and behaviors, and thus could also have important biological applications.

Controlling Photocatalytic Activity by Self‐Assembly – Tuning Perylene Bisimide Photocatalysts for the Hydrogen Evolution Reaction

AbstractAmino acid functionalized perylene bisimides (PBIs) form self‐assembled structures in solution, the nature of which depends on the local environment. Using a high‐throughput photocatalysis setup, five PBIs are studied for the hydrogen evolution reaction (HER) under a range of conditions (pH and hole scavenger concentration) across 350 experiments to explore the relationship between supramolecular structure and photocatalytic activity. Using small angle X‐ray scattering (SAXS), NMR spectroscopy and ultraviolet‐visible (UV‐vis) absorption spectroscopy, it is shown that photocatalytic activity is determined by the nature of the self‐assembled aggregate that is formed, demonstrating the potential of self‐assembly to tune activity. There is a clear correlation between the presence of charged flexible cylindrical aggregates and the occurrence of photocatalytic H2 production, with UV–vis spectroscopy indicating that the most active structure type has a distinctive form of π‐aggregation which is proposed to enable efficient charge separation across multiple PBI units.

Goethite effects on transport and activity of lysozyme with humic acid in quartz sand

Proteins play important roles in environmental processes and are essential to soil and ecosystem health. However, little is known about the transport of proteins, especially enzymes, in natural environments with significant heterogeneity. Here, we investigated the transport and retention of a model enzyme lysozyme (LSZ) with/without the presence of purified Aldrich humic acid (PAHA) by saturated transport experiments in heterogeneous sand columns containing mixtures of uncoated (QS) and goethite-coated quartz sand (GQS) with (GQS/(QS + GQS)) mass fractions w = 0, 0.1, 0.3 and 0.5. The impact of different PAHA/LSZ mass ratios (f = 0, 0.2 and 0.4) on LSZ mobility was also examined in a GQS/QS column (w = 0.3). The results revealed that the transport of pure LSZ and PAHA decreased with increasing w from 0 to 0.5, largely because of increased microscopic roughness and enhanced patch controlled electrostatic attraction between sand grains and LSZ or PAHA. Furthermore, an overall decline of the breakthrough curve plateau was observed when f was fixed as 0.2 at different w due to progressive PAHA-LSZ aggregation and physical straining. In these GQS/QS columns, positively charged LSZ broke through earlier because goethite of GQS tended to first capture negatively charged PAHA and PAHA-LSZ complexes/aggregations. At w = 0.3, LSZ retention was increased with increasing f and the retention profiles exhibited a hyper-exponential shape. Due to the preferential retention of overall negatively charged and larger-sized PAHA-LSZ aggregates in the GQS/QS column, the enzyme activity of retained LSZ was lower than that in the effluent and decreased with increasing w. The synergistic effect of humic acid and iron (hydr)oxide coating decreased LSZ mobility. These findings may facilitate a better understanding of the transport and retention of proteins in heterogeneous natural environment, and help to deal with the potential environmental risk posed by hazardous proteins.