Charged Shell Research Articles

Symmetrized Drude Oscillator Force Fields Improve Numerical Performance of Polarizable Molecular Dynamics

Drude oscillator potentials are a popular and computationally efficient class of polarizable models that represent each polarizable atom as a positively charged Drude core harmonically bound to a negatively charged Drude shell. We show that existing force fields that place all non-Coulomb forces on the Drude core and none on the shell inadvertently couple the dipole to non-Coulombic forces. This introduces errors where interactions with neutral particles can erroneously induce atomic polarization, leading to spurious polarizations in the absence of an electric field, exacerbating violations of equipartition in the employed Carr-Parinello scheme. A suitable symmetrization of the interaction potential that correctly splits the force between the Drude core and shell can correct this shortcoming, improving the stability and numerical performance of Drude oscillator-based simulations. The symmetrization procedure is straightforward and only requires the rescaling of a few force field parameters.

Behavior and bioactive properties of aqueous L-cysteine–AgNO3 solution at different pH

Polypeptide-like supramolecular aggregates are formed in aqueous cysteine–AgNO3 solution. At low pH, their positively charged shell consists of several layers of cysteine–Ag+ complexes held by hydrogen bonds; with an increase in pH, the particles aggregate at isoelectric point; while at higher pH, the shell acquires negative charge and starts being destroyed. The pH control has been demonstrated for cytotoxic effect of the solution against MCF-7 breast cancer cells

Bacteria-Induced Colloidal Encapsulation for Probiotic Oral Delivery

Probiotic oral delivery has crucial implications in biomedical engineering, but its oral bioavailability remains unsatisfactory because of the limited survival and colonization of probiotics in the harsh gastrointestinal tract. Here, a bacteria-induced encapsulation strategy is achieved by assembling metastable colloids to enhance the oral bioavailability of probiotics. The colloids (NTc) composed of amino-modified poly-β-cyclodextrin and tannic acid are formed based on the balance of host-guest interaction-driven attraction and electrostatic repulsion between colloids. Negatively charged probiotics electrostatically attract positively charged NTc to break the balance and induce further assembly surrounding the probiotics. Through a facile one-step mixing, 97% of bacteria are rapidly encapsulated into NTc shells within 10 s, with a high utilization rate of feeding colloids of 91%. More importantly, we show that the compact, thick, and positively charged NTc shells synergistically endow the encapsulated probiotics with strong resistance against simulated gastric fluid with an excellent survival rate of up to 19%, 7500 times superior to the commercial enteric material L100. Moreover, owing to the dynamically noncovalent and self-adaptive nature of host-guest interactions, NTc shells support the proliferation of the encapsulated EcN comparable with that of the naked EcN. In vitro and in vivo experiments also confirm that the NTc-encapsulated probiotics possess durable intestinal adhesion, continuous proliferation activity, enhanced oral bioavailability, good oral biosafety, and excellent therapeutic efficacy in a colitis mouse model. This facile bacteria-induced colloidal encapsulation strategy may extend to various microbes as oral bioagents for treating various diseases.

POM@PMO plastic electrode for phosphate electrochemical detection: a further improvement of the detection limit

The development of a highly sensitive electrochemical sensor (E-sensor) is described based on stand-alone plastic electrodes (PE) for phosphate detection, being an essential nutrient in the marine environment. The detection mechanism is based on the chemical affinity between polyoxomolybdate anions (POM) and orthophosphate to form an electroactive phosphomolybdate complex. The custom-made E-sensor was formulated with an organic octamolybdate derivative (TBA4Mo8O26) incorporated with periodic mesoporous organosilica (PMO) to obtain a significant improvement in the analytical performances of phosphate determination. This POM@PMO combination was found to be advantageous in the determination of low concentrations of phosphate in standard solutions ranging from 1 to 500 nM, using square wave voltammetry as the detection technique. This sensitivity enhancement can be attributed to the effect of hydrophobic PMO in loading more POM moieties, owing to its highly porous structure and charged shell. Consequently, the POM@PMO-PE sensor achieved a competitive sensitivity of 4.43 ± 0.14 μA.nM−1.cm−2 and a limit of detection of 0.16 nM with good selectivity against silicates. Finally, seawater and treated wastewater samples have been tested to validate the sensor response in comparison to the official method of phosphate determination.Graphical abstract

Coating with cationic inulin enhances the drug release profile and in vitro anticancer activity of lecithin-based nano drug delivery systems

Core-shell structured lipidic nanoparticles (LNPs) were developed using lecithin sodium acetate (Lec-OAc) ionic complex as a core unit and quaternized inulin (QIn) as the shell part. Inulin (In) was modified using glycidyl trimethyl ammonium chloride (GTMAC) as a positively charged shell part and used for coating the negatively surface charged Lec-OAc. The critical micelle concentration (CMC) of the core was determined as 1.047 × 10−4 M, which is expected to provide high stability in blood circulation as a drug-carrying compartment. The amounts of curcumin (Cur) and paclitaxel (Ptx) loaded to LNPs (CurPtx-LNPs), and quaternized inulin-coated LNPs (Cur-Ptx-QIn-LNPs) were optimized to obtain mono-dispersed particles with maximum payload. The total amount of 2.0 mg of the drug mixture (1 mg Cur and 1 mg Ptx) was the optimized quantity for QIn-LNPs and CurPtx-QIn-LNPs due to the favorable physicochemical properties determined by dynamic light scattering (DLS) studies. This inference was confirmed by differential scanning calorimeter (DSC), and Fourier-transform infrared (FT-IR). SEM and TEM images clearly revealed the spherical shapes of LNPs and QIn-LNPs, and QIn covered the LNPs completely. The cumulative release measurements of Cur and Ptx from CurPtx-QIn-LNPs, along with the kinetic studies, showed a significant decrease in the release period of drug molecules with the effect of the coating. At the same time, Korsmeyer-Peppas was the best diffusion-controlled release model. Coating of the LNPs with QIn increased the cell-internalization of NPs to the MDA-MB-231 breast cancer cell lines, resulting in a better toxicity profile than the empty LNPs.

Dye-induced photoluminescence quenching of quantum dots: role of excited state lifetime and confinement of charge carriers.

We investigate the role of quantum confinement and photoluminescence (PL) lifetime of photoexcited charge carriers in semiconductor core/shell quantum dots (QDs) via PL quenching due to surface modification. Surface modification is controlled by varying the number of dye molecules adsorbed onto the QD shell surface forming QD-dye nanoassemblies. We selected CuInS2/ZnS (CIS) and InP/ZnS (InP) core/shell QDs exhibiting relatively weak (664 meV) and strong (1194 meV) confinement potentials for the conduction band electron. Moreover, the difference in the emission mechanism gives rise to a long and short excited state lifetime of CIS (ca. 290 ns) and InP (ca. 37 ns) QDs. Dye molecules of different ionic characters (rhodamine 575: zwitterionic and rhodamine 560: cationic) are used as quenchers. A detailed analysis of Stern-Volmer data shows that (i) quenching is generally more pronounced in CIS-dye assemblies as compared to InP-dye assemblies, (ii) dynamic quenching is dominating in all QD-dye assemblies with only a minor contribution from static quenching and (iii) the cationic dye shows a stronger interaction with the QD shell surface than the zwitterionic dye. Observations (i) and (ii) can be explained by the differences in the amplitude of the electronic component of the exciton wavefunction near the dye binding sites in both QDs, which results in the breaking up of the electron-hole pair and favors charge trapping. Observation (iii) can be attributed to the variations in electrostatic interactions between the negatively charged QD shell surface and the cationic and zwitterionic dyes, with the former exhibiting a stronger interaction. Moreover, the long lifetime of CIS QDs facilitates us to easily probe different time scales of the trapping processes and thus differentiate the origins of static and dynamic quenching components that appear in the Stern-Volmer analysis.

Silica-coated gold nanorods biofunctionalization for localized surface plasmon resonance (LSPR) biosensing

We introduce here the engineering of nanobiosensors designed from gold nanorods coated with an ultrathin layer of silica (AuNR@SiO2) and biofunctionalized with antibodies for the Localized Surface Plasmon Resonance (LSPR) biosensing of proteins. Despite the outstanding properties of AuNRs, their use for LSPR biosensing is limited due to the presence of the surfactant cetyltrimethylammonium bromide (CTAB) – mandatory for their synthesis - which forms a strongly-bounded and positively-charged bilayer at their surface and significantly complicates their bio-functionalization. When coated with a thin layer of silica, these nanomaterials exhibit an improved sensitivity to refractive index change which augurs for better analytical performances. Here, we undertook an in-depth investigation of the biofunctionalization of AuNR@SiO2via three different routes to design and test a label-free LSPR biosensor operating in solution. In the first route, we took advantage of the negatively charged external silica shell to immobilize anti-rabbit IgG antibody by electrostatic physisorption. In the second and third routes, the silica surface was reacted with thiol or aldehyde terminated silanes, subsequently utilized to covalently attach anti-rabbit IgG antibody to the surface. The resulting nanoprobes were characterized by a wide range of physical methods (TEM, XPS, DLS, ELS and UV-Visible spectroscopy) then tested for the biosensing of rabbit-IgG. The three nanobiosensors maintain an excellent colloidal stability after analyte recognition and exhibit extremely high analytical performances in terms of specificity and dynamic range, with an LoD down to 12 ng/mL.

Off-axis electric field due to cylindrical geometries of charge distribution

Off-axis electric field due to cylindrical distribution of charge is studied in various geometries, including solid cylinder, cylindrical shell, disk, and ring. The electric fields of the charged solid cylinder and cylindrical shell can be found by numerical calculations, but closed forms expressed in terms of elliptic integrals are derived for the charged disk and ring. By investigating the radial and axial components of the electric fields systematically we reveal many interesting and new features that are implicit or unseen in the ordinary approach based on the cylindrical symmetry.

Bouncing inside the horizon and scrambling delays

We study charged perturbations of the thermofield double state dual to a charged AdS black hole. We model the perturbation by a massless charged shell in the bulk. Unlike the neutral case, all such shells bounce at a definite radius, which can be behind the horizon. We show that the standard “shock wave” calculation of a scrambling time indicates that adding charge increases the scrambling time. We then give two arguments using the bounce that suggest that scrambling does not actually take longer when charge is added, but instead its onset is delayed. We also construct a boundary four point function which detects whether the shell bounces inside the black hole.

Electrically charged spherical matter shells in higher dimensions: Entropy, thermodynamic stability, and the black hole limit

We study the thermodynamic properties of a static electrically charged spherical thin shell in $d$ dimensions by imposing the first law of thermodynamics on the shell. The shell is at radius $R$, inside it the spacetime is Minkowski, and outside it the spacetime is Reissner-Nordstr\"om. We obtain that the shell thermodynamics is fully described by giving two additional reduced equations of state, one for the temperature and another for the electrostatic potential. We choose the equation of state for the temperature as a power law in the gravitational radius $r_+$ with exponent $a$, such that the $a=1$ case gives the temperature of a shell with black hole thermodynamic properties, and for the electrostatic potential we choose an equation of state characteristic of a Reissner-Nordstr\"om black hole spacetime. The entropy of the shell is found to be proportional to $A_+^a$, where $A_+$ is the gravitational area corresponding to $r_+$, with $a>0$. We are then able to perform the black hole limit $R=r_+$, find the Smarr formula, and recover the thermodynamics of a $d$-dimensional Reissner-Nordstr\"om black hole. We study the intrinsic thermodynamic stability of the shell with the chosen equations of state. We obtain that for $0<a\leq \frac{d-3}{d-2}$ all the configurations of the shell are thermodynamically stable, for $\frac{d-3}{d-2}<a<1$ stability depends on the mass and electric charge, and for $a>1$ all the configurations are unstable, except for the shell at its own gravitational radius, which is marginally stable. We rewrite the stability conditions in terms of laboratory variables. We find that the sufficient condition for the stability of these shells is when the isothermal electric susceptibility $\chi_{p,T}$ is positive, marginal stability happening when this quantity is infinite, and instability arising for configurations with a negative electric susceptibility.

An Angular Method to Calculate the Electric Field of a Long Cylindrical Shell

The electric field inside a uniformly charged long cylindrical shell is a standard example discussed in introductory university physics. The field is zero inside the cylinder; outside of the cylinder, the field behaves like a long wire at the center carrying the same amount of charge per unit length, analogous to that of a uniformly charged spherical shell, typically referred to as Newton’s shell theorem. It is usually proven with the use of Gauss’s law and cylindrical symmetry of the electric field. A more direct proof by integration is lacking at this level. In fact, students often have difficulties visualizing intuitively why the field at off-center points is cancelled out completely and behaves like a line charge at the center on the outside.

Electric field control of labyrinth domain structures in core-shell ferroelectric nanoparticles

In the framework of the Landau-Ginzburg-Devonshire (LGD) approach, we studied the possibility of controlling the polarity and morphology of equilibrium domain structures by a homogeneous external electric field in a nanosized ferroelectric core covered with an ultrathin shell of screening charge. Under certain screening lengths and core sizes, the minimum of the LGD energy, which consists of Landau-Devonshire energy, Ginzburg polarization gradient energy, and electrostatic terms, leads to the spontaneous appearance of stable labyrinth domain structures in the core. The labyrinths evolve from an initial polarization distribution consisting of arbitrarily small randomly oriented nanodomains. The equilibrium labyrinth structure is weakly influenced by details of the initial polarization distribution, such that one can obtain a quasicontinuum of nearly degenerate labyrinth structures, whose number is limited only by the mesh discretization density. Applying a homogeneous electric field to a nanoparticle with labyrinth domains, and subsequently removing it, allows inducing changes to the labyrinth structure, as the maze polarity is controlled by a field projection on the particle polar axis. Under specific conditions of the screening charge relaxation, the quasistatic dielectric susceptibility of the labyrinth structure can be negative, potentially leading to a negative capacitance effect. Considering the general validity of the LGD approach, we expect that an electric field control of labyrinth domains is possible in many spatially confined nanosized ferroics, which can be potentially interesting for advanced cryptography and modern nanoelectronics.

ELF-VLF Transmissions via Motion-Induced Radiation of Charges

Mechanical antennas have garnered interest as a potential method of transmitting extremely low-frequency (ELF) to very-low-frequency (VLF) radiation in a manner that possesses a high efficiency of radiation and a low form factor. In this article, we investigate these claims by solving for the exact field solutions for one particular example, a rotational-oscillating charged thin spherical shell. The field solutions allow the analysis of the radiation pattern, radiation efficiency, and spectral output as a function of several geometric and kinematic quantities of the sphere. The results indicate that high efficiency with a low form-factor appears to be plausible, assuming that the required mechanical conditions for the motion can be achieved.

Well-Defined pH-Responsive Self-Assembled Block Copolymers for the Effective Codelivery of Doxorubicin and Antisense Oligonucleotide to Breast Cancer Cells.

The worldwide steady increase in the number of cancer patients motivates the development of innovative drug delivery systems for combination therapy as an effective clinical modality for cancer treatment. Here, we explored a design concept based on poly(ethylene glycol)-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(2-hydroxyethyl methacrylate-formylbenzoic acid) [PEG-b-PDMAEMA-b-P(HEMA-FBA)] for the dual delivery of doxorubicin (DOX) and GTI2040 (an antisense oligonucleotide for ribonucleotide reductase inhibition) to MCF-7 breast cancer cells. PEG-b-PDMAEMA-b-PHEMA, the precursor copolymer, was prepared through chain extensions from a PEG-based macroinitiator via two consecutive atom transfer radical polymerization (ATRP) steps. Then, it was modified at the PHEMA block with 4-formylbenzoic acid (FBA) to install reactive aldehyde moieties. A pH-responsive polymer-drug conjugate (PDC) was obtained by conjugating DOX to the polymer structure via acid-labile imine linkages, and subsequently self-assembled in an aqueous solution to form DOX-loaded self-assembled nanoparticles (DOX-SAN) with a positively charged shell. DOX-SAN condensed readily with negatively charged GTI2040 to form GTI2040/DOX-SAN nanocomplexes. Gel-retardation assay confirmed the affinity between GTI2040 and DOX-SAN. The GTI2040/DOX-SAN nanocomplex at N/P ratio of 30 exhibited a volume-average hydrodynamic size of 136.4 nm and a zeta potential of 21.0 mV. The pH-sensitivity of DOX-SAN was confirmed by the DOX release study based on the significant cumulative DOX release at pH 5.5 relative to pH 7.4. Cellular uptake study demonstrated favorable accumulation of GTI2040/DOX-SAN inside MCF-7 cells compared with free GTI2040/DOX. In vitro cytotoxicity study indicated higher therapeutic efficacy of GTI2040/DOX-SAN relative to DOX-SAN alone because of the downregulation of the R2 protein of ribonucleotide reductase. These outcomes suggest that the self-assembled pH-responsive triblock copolymer is a promising platform for combination therapy, which may be more effective in combating cancer than individual therapies.

Dynamics of spherical charged dust shells in de Sitter space

We study the dynamics of charged, spherically symmetric dust shells in the presence of a positive cosmological constant. We find generalizations of the well-known solutions in asymptotically flat spacetime, in particular orbits into ``parallel universes,'' but also new solutions corresponding to a ``bounce'' of the shell before an event horizon has formed. We also discuss ``bubble'' solutions, in which a charged shell and an oppositely charged singularity are spontaneously created and annihilated.

Enhancing Efficiency of Nonfullerene Organic Solar Cells via Using Polyelectrolyte-Coated Plasmonic Gold Nanorods as Rear Interfacial Modifiers.

Sufficient sunlight absorption and exciton generation are critical for developing efficient nonfullerene organic solar cells (OSCs). In this work, polyelectrolyte polystyrenesulfonate (PSS)-coated plasmonic gold nanorods (GNRs@PSS) were incorporated, for the first time, into the inverted nonfullerene OSCs as rear interfacial modifiers to improve sunlight absorption and charge generation via the near-field plasmonic and backscattering effects. The plasmonic GNRs effectively improved the sunlight absorption and enhanced the charge generation. Meanwhile, the negatively charged PSS shell ensured the uniform dispersion of the GNRs on the surface of the photoactive layer, optimized the interfacial contact, and further promoted the hole transport to the electrode. These concerted synergistic effects augmented the efficiency (10.11%) by nearly 20% relative to the control device (8.47%). Remarkably, the ultrathin (∼2.2 nm) organic layer on the surface of GNRs was closely examined by acquiring the carbon contrast image through energy-filtered transmission electron microscopy (EF-TEM), which clearly confirmed the coating uniformity from the side to end-cap of GNRs. The surface plasmon resonance (SPR) effect of the GNRs@PSS on the surface of the photoactive layer was unprecedentedly mapped by photoinduced force microscopy (PiFM) under the illumination of a tunable wavelength supercontinuum laser mimicking sunlight. Furthermore, investigations into the effect of size, surface coverage, and incorporation location of GNRs@PSS on the performance of OSCs revealed that the appropriate design and incorporation of the plasmonic nanostructures are crucial, otherwise the performance can be decreased, as evidenced in the case of front interface integration.

Versatile Diblock Polyampholytes Can Form Two Types of Charged and Internally Structured Core-Shell Particles by Complexation with Cationic or Anionic Surfactants.

We used diblock poly(acrylic acid)-b-poly(2-dimethylamino ethyl methacrylate) (PAA-b-PDMAEMA) polyampholytes to prepare core-shell complexes with ionic surfactants. The dispersions have been characterized by means of small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (Cryo-TEM), dynamic light-scattering, and zeta potential methods. Using cationic or anionic surfactants it is possible to produce particles with either positively or negatively charged shells, both having an internal liquid-crystalline core structure. For the different systems, different preparation protocols were found to be successful to produce stable and reproducible particles. The particle morphologies depend on the surfactant used. Complexes with the cationic surfactant hexadecyltrimethylammonium (CTA+) form oblate particles, while complexes with dodecyl sulfate (DS-) form cylindrical rods. In both complexes, the smallest dimension of the core does not exceed twice the block length of the core-forming polymer block. For the particles with CTA+, nonelectrostatic attractive interactions among the PDMAEMA chains in the shells seem to be present, affecting the particle shape. In both types of particles, the surfactant in the core forms rod-like aggregates, arranged in a two-dimensional hexagonal structure with the surfactant rods aligned with the axis of rotational symmetry in the particle. With charged polymer chains in the shell, the aggregates present a striking stability over time, displaying no change in particle size over the time scale investigated (10 months). Nevertheless, the aggregates are highly dynamic in nature, and their shapes and structures can be changed dramatically in dispersion, without intermediate precipitation, by changes in the composition of the medium. Specifically, a transition from aggregates with cationic surfactant to aggregates with anionic surfactant can be achieved.

Core-crosslinked micelles with a poly-anionic poly(styrene sulfonate)-based outer shell made by RAFT polymerization

Core-crosslinked micelles (CCMs) with a permanently charged anionic shell of sodium poly(styrene sulfonate) (PSS–Na+) chains have been developed by a convergent three-step one-pot RAFT polymerization starting with 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA, R0-SC(S)SnPr) as chain transfer agent, which includes polymerization-induced self-assembly (PISA) in the second step. The final crosslinking step of the R0-(SS-Na+)x-b-Sty-SC(S)SnPr diblock chains was carried out with diethylene glycol dimethacrylate (DEGDMA), either diluted into styrene (DEGDMA/St = 10:90) or neat. The morphology of the intermediate micelles and of the final CCM particles was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM) as a function of the relative degrees of polymerizations for the shell, core, and crosslinking blocks. Conformational instability was observed for the aqueous dispersions of the diblock micelles, especially with the shorter PSt blocks, yielding equilibria with single chains and large agglomerates. However, crosslinking led to well-defined CCMs with narrow size distributions for the optimized polymer compositions. The DLS analysis in a compatibilizing 60:40 THF/H2O solvent mixture demonstrates that the final step of the polymer synthesis has quantitatively crosslinked all diblock arms.

Thermodynamical and dynamical stability of a self-gravitating charged thin shell

A study of the thermodynamical and dynamical stability of self-gravitating charged shells is presented. The matter on the shell is described by a barotropic equation of state, and the charge is assumed to be proportional to the mass. For a given form of the entropy of the matter on the shell, it is shown that strong restrictions on the states of the shell follow from the imposition of both types of stability plus the condition that the speed of sound is less than one, in some cases leading to the absence of stable states.

Microscale Thermophoresis Assay: A Powerful Method to Quantify Protein-Nucleic Acid and Protein-Protein Interactions.

Plant viruses are among the most disastrous pathogens that cause enormous losses in crop yield and crop quality, threatening food security worldwide. These losses are attributed to virus-induced plant physiological disorders and diseases. During the ever-evolving arm race between viruses and their hosts, viruses have evolved multiple strategies to disrupt plant fortification, for example, taking advantage of RNA silencing and plant hormone pathways. Microscale thermophoresis (MST) assay arises as a rapid and precise method to identify the interactions between biomolecules including host and viral factors from plant virus infections.The technique is based on the motion of molecules in temperature gradients, which is termed thermophoresis, and depends on the binding-induced changes in molecular size, charge, and solvation shell. This chapter provides a detailed protocol describing the application of MST assays in analyzing protein-nucleic acid and protein-protein interactions, taking the Rice stripe virus (RSV )-encoded nonstructural protein 3 (NS3) that recognizes primary miR528 transcript (pri-miR528) and Rice dwarf virus (RDV )-encoded capsid protein P2 that recognizes OsIAA10 as examples.