Net Electrostatic Charge Research Articles

Surface hydrophobicity and catalytic performance of cerium incorporated HZSM-5 zeolite for conversion of bio-ethanol

Cerium incorporated HZSM-5 (CeHZSM-5) catalyst prepared by impregnation method was tested for aqueous ethanol conversion at 200–400 °C. The CeHZSM-5 catalyst was found to be very active (21.02 %Conversion), compared to the parent HZSM-5 catalyst (9.39 %Conversion), especially at low reaction temperatures (200 °C) and when fed with high water content (80 wt% ethanol). FTIR, FT-Raman, DR-UV, NH3-TPD, IPA-TPD, DSC and contact angle techniques reveal that the incorporation of cerium species into zeolites results in the acidity and hydrophilic/hydrophobic nature. Cerium species are thought to tend to migrate into ZSM-5 channels and associate with the zeolite framework. As a result, the net electrostatic charge decreases due to the presence of tetrahedral cerium atoms. Therefore, the CeHZSM-5 exhibits a hydrophobic character, compared to the parent one. The decrease in competitive adsorption of water versus ethanol feed at the Brønsted acid site may lead to an increase in CeHZSM-5 catalyst activity.

Platelet factor 4 improves survival in a murine model of antibiotic-susceptible and methicillin-resistant Staphylococcus aureus peritonitis.

The complement receptor CR3, also known as integrin Mac-1 (CD11b/CD18), is one of the major phagocytic receptors on the surface of neutrophils and macrophages. We previously demonstrated that in its protein ligands, Mac-1 binds sequences enriched in basic and hydrophobic residues and strongly disfavors negatively charged sequences. The avoidance by Mac-1 of negatively charged surfaces suggests that the bacterial wall and bacterial capsule possessing net negative electrostatic charge may repel Mac-1 and that the cationic Mac-1 ligands can overcome this evasion by acting as opsonins. Indeed, we previously showed that opsonization of Gram-negative Escherichia coli with several cationic peptides, including PF4 (Platelet Factor 4), strongly augmented phagocytosis by macrophages. Here, we investigated the effect of recombinant PF4 (rPF4) on phagocytosis of Gram-positive Staphylococcus aureus in vitro and examined its impact in a mouse model of S. aureus peritonitis. Characterization of the interaction of rPF4 with nonencapsulated and encapsulated S. aureus showed that rPF4 localizes on the bacterial surface, thus making it available for Mac-1. Furthermore, rPF4 did not have direct bactericidal and bacteriostatic activity and was not toxic to host cells. rPF4 enhanced phagocytosis of S. aureus bioparticles by various primary and cultured Mac-1-expressing leukocytes by several folds. It also increased phagocytosis of live nonencapsulated and encapsulated bacteria. Notably, the augmentation of phagocytosis by rPF4 did not compromise the intracellular killing of S. aureus by macrophages. Using a murine S. aureus peritonitis model, we showed that treatment of infected mice with rPF4 caused a significant increase in the clearance of antibiotic-susceptible S. aureus and its methicillin-resistant (MRSA) variant and markedly improved survival. These findings indicate that rPF4 binding to the bacterial surface circumvents its antiphagocytic properties, improving host defense against antibiotic-susceptible and antibiotic-resistant bacteria.

Static electricity passively attracts ticks onto hosts.

Most terrestrial animals naturally accumulate electrostatic charges, meaning that they will generate electric forces that interact with other charges in their environment, including those on or within other organisms. However, how this naturally occurring static electricity influences the ecology and life history of organisms remains largely unknown.1 Mammals, birds, and reptiles are known to carry appreciable net electrostatic charges, equivalent to surface potentials on the order of hundreds to tens of thousands of volts.1,2,3,4,5,6,7 Therefore, we hypothesize that their parasites, such as ticks, are passively attracted onto their surfaces by electrostatic forces acting across air gaps. This biophysical mechanism is proposed by us to assist these ectoparasites in making contact with their hosts, increasing their effective "reach" because they are otherwise incapable of jumping. Herein, experimental and theoretical evidence show that the tick Ixodes ricinus (Figure1A) can close the gap to their hosts using ecologically relevant electric fields. We also find that this electrostatic interaction is not significantly influenced by the polarity of the electric field, revealing that the mechanism of attraction relies upon induction of an electrical polarization within the tick, as opposed to a static charge on its surface. These findings open a new dimension to our understanding of how ticks, and possibly many other terrestrial organisms, find and attach to their hosts or vectors. Furthermore, this discovery may inspire novel solutions for mitigating the notable and often devastating economic, social, and public health impacts of ticks on humans and livestock.8,9,10,11,12,13,14,15.

Nano and micro-vesicle diffusion through proteins, electrostatics mediate its interactions.

The primary biochemical communication in the body is mediated by vesicles, from energy transport to neural signals. Understanding the driving forces of its diffusion will proportionate light to comprehend the nature of some diseases. In this work, we investigate the diffusion of nano and microvesicles in a bovine serum albumin solution, as we alter their temperature and electrostatic charge. Their molecular interactions were studied by differential scanning calorimetry and its short-long range interactions by dynamic light scattering and video tracking. Results showed that the phase transition of the lipids alters its diffusion drastically and that the nano-size vesicles with net negative electrostatic charge are the most reactive to the protein.

Charge transfer and bipolar charging of particles in a bubbling fluidized bed

Particle–particle and particle–wall collisions in gas–solid fluidized beds lead to charge accumulation on particles. This work evaluated the effect of fluidization time on charge transfer and bipolar charging (charge separation) and their influence on hydrodynamic structures in a fluidized bed. Experiments were performed with glass beads and polyethylene particles in a glass column. The pressure fluctuations and net electrostatic charge of particles were measured during fluidization. Wavelet and short-time Fourier transforms were used to analyze pressure fluctuations. The results revealed that bipolar charging is the dominant tribocharging mechanism in a bed of glass beads. Bipolar charging in a bed of particles with a narrow size distribution does not affect either hydrodynamic structures or the transition velocity to the turbulent regime. A large difference between the work functions of the wall and particle in the bed of polyethylene particles leads to high charge transfer. Formation of a stagnant particle layer on the wall eventually causes the energy of macro-structures to increase to its maximum. At longer fluidization times, the macro-structural energy decreases and bubbles shrink until the electrostatic charge reaches the equilibrium level. These results well describe the effect of fluidization time on hydrodynamic structures.

What Are We Missing by Not Measuring the Net Charge of Proteins?

The net electrostatic charge (Z) of a folded protein in solution represents a bird's eye view of its surface potentials-including contributions from tightly bound metal, solvent, buffer, and cosolvent ions-and remains one of its most enigmatic properties. Few tools are available to the average biochemist to rapidly and accurately measure Z at pH≠pI. Tools that have been developed more recently seem to go unnoticed. Most scientists are content with this void and estimate the net charge of a protein from its amino acid sequence, using textbook values of pKa . Thus, Z remains unmeasured for nearly all folded proteins at pH≠pI. When marveling at all that has been learned from accurately measuring the other fundamental property of a protein-its mass-one wonders: what are we missing by not measuring the net charge of folded, solvated proteins? A few big questions immediately emerge in bioinorganic chemistry. When a single electron is transferred to a metalloprotein, does the net charge of the protein change by approximately one elementary unit of charge or does charge regulation dominate, that is, do the pKa values of most ionizable residues (or just a few residues) adjust in response to (or in concert with) electron transfer? Would the free energy of charge regulation (ΔΔGz ) account for most of the outer sphere reorganization energy associated with electron transfer? Or would ΔΔGz contribute more to the redox potential? And what about metal binding itself? When an apo-metalloprotein, bearing minimal net negative charge (e.g., Z=-2.0) binds one or more metal cations, is the net charge abolished or inverted to positive? Or do metalloproteins regulate net charge when coordinating metal ions? The author's group has recently dusted off a relatively obscure tool-the "protein charge ladder"-and used it to begin to answer these basic questions.

Tl(I) sorption behavior on birnessite and its implications for mineral structural changes

Abstract Thallium is the most toxic regulated metallic ion in soil and water. Previous work in soil samples contaminated by metallurgical wastes has revealed a very high correlation between extracted Tl and Mn in the reducible mineral fractions, which suggests a high geochemical affinity between Tl and Mn oxides, once Tl has been released from the primary minerals it is originally associated with (aluminosilicates and sulfides). The goal of the present work was to determine the behavior and mechanisms of thallium (I) sorption on Mn(IV)-birnessites, focusing on expanding the conditions previously investigated, by using two synthetic poorly-crystalline preparations of this mineral that are the closest analogs to biologically-produced Mn oxides, but differ greatly in their particle sizes; and by testing the effects of a wide range of pH values and Tl(I) concentrations, to simulate a large variability in geochemical conditions. To achieve this, we performed Tl(I) sorption isotherms on clean preparations of both birnessites at three different pH values (4, 6 and 8) and X ray Absorption Spectroscopy (XAS), X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and Specific Surface Area (SSA) analyses on selected samples. Thallium (I) sorption to the birnessites consists of a prevailing irreversible oxidation mechanism, with retention of the Tl(III) produced, mainly over vacant layer sites, and eventual formation of the mineral avicennite (Tl2O3) at high loadings and pH. Thallium (I) was increasingly sorbed/oxidized at all pH values, but its extent increased as pH was raised, contrary to what the redox reaction suggests, where protons contribute as reacting agents. The sorption/oxidation reaction was also independent of the birnessite initial particle size or vacancy content. This strongly suggests that the net negative electrostatic charge of the birnessite plays a major role in the reaction, and therefore, the sorption part of the mechanism is the limiting and prevailing step of the overall process; however, since Tl(I) enters into the mineral structure and may potentially access all internal Mn(IV) available, the redox reaction appears to be boundless, showing extremely high capacities for Tl(I) oxidation. Finally, at high concentrations of the Tl(III) formed, and apparently coinciding with the formation of avicennite (Tl2O3), a general delamination of the birnessite layered structure was provoked adding to its gradual dissolution.

Direct Measurement of Charge Regulation in Metalloprotein Electron Transfer.

Determining whether a protein regulates its net electrostatic charge during electron transfer (ET) will deepen our mechanistic understanding of how polypeptides tune rates and free energies of ET (e.g., by affecting reorganization energy, and/or redox potential). Charge regulation during ET has never been measured for proteins because few tools exist to measure the net charge of a folded protein in solution at different oxidation states. Herein, we used a niche analytical tool (protein charge ladders analyzed with capillary electrophoresis) to determine that the net charges of myoglobin, cytochrome c, and azurin change by 0.62±0.06, 1.19±0.02, and 0.51±0.04 units upon single ET. Computational analysis predicts that these fluctuations in charge arise from changes in the pK a values of multiple non‐coordinating residues (predominantly histidine) that involve between 0.42–0.90 eV. These results suggest that ionizable residues can tune the reactivity of redox centers by regulating the net charge of the entire protein–cofactor–solvent complex.

Direct Measurement of Charge Regulation in Metalloprotein Electron Transfer

AbstractDetermining whether a protein regulates its net electrostatic charge during electron transfer (ET) will deepen our mechanistic understanding of how polypeptides tune rates and free energies of ET (e.g., by affecting reorganization energy, and/or redox potential). Charge regulation during ET has never been measured for proteins because few tools exist to measure the net charge of a folded protein in solution at different oxidation states. Herein, we used a niche analytical tool (protein charge ladders analyzed with capillary electrophoresis) to determine that the net charges of myoglobin, cytochrome c, and azurin change by 0.62±0.06, 1.19±0.02, and 0.51±0.04 units upon single ET. Computational analysis predicts that these fluctuations in charge arise from changes in the pKa values of multiple non‐coordinating residues (predominantly histidine) that involve between 0.42–0.90 eV. These results suggest that ionizable residues can tune the reactivity of redox centers by regulating the net charge of the entire protein–cofactor–solvent complex.

Structural and vibrational characteristics of a non-linear optical material 3-(4-nitrophenyl)-1-(pyridine-3-yl) prop-2-en-1-one probed by quantum chemical computation and spectroscopic techniques

Chalcone and its derivatives are well-known for their high non-linear optical behavior and charge transfer characteristics. The effectiveness of charge transfer via ethylenic group and increase in NLO response of the chalcone upon substitutions are of great interest. The present study focuses the structural, charge transfer and non-linear optical properties of a new chalcone derivative “3-(4-nitrophenyl)-1-(pyridine-3-yl) prop-2-en-1-one” (hereafter abbreviated as 4 NP3AP). To accomplish this task, we have incorporated the experimental FT-IR, FT-Raman and UV–vis spectroscopic studies along with quantum chemical calculations. The frequency assignments of peaks in IR and Raman have been done on the basis of potential energy distribution and the results were compared with the earlier reports on similar kind of molecules. For obtaining the electronic transition details of 4 NP3AP, UV–vis spectrum has been simulated by considering both gaseous and solvent phase using time-dependent density functional theory (TD-DFT). The HOMO-LUMO energy gap, most important factor to be considered for studying charge transfer properties of the molecule has been calculated. The electron density surface map corresponding to the net electrostatic point charges has been generated to obtain the electrophilic and nucleophilic sites. The charge transfer originating from the occupied (donor) and unoccupied (acceptor) molecular orbitals have been analyzed with the help of natural bond orbital theory. Moreover, the estimation of second-hyperpolarizability of the molecule confirms the non-linear optical behavior of the molecule.

Macromolecule-Network Electrostatics Controlling Delivery of the Biotherapeutic Cell Modulator TIMP-2.

Tissue inhibitor of metalloproteinase 2 (TIMP-2) is an endogenous 22 kDa proteinase inhibitor, demonstrating antitumorigenic, antimetastatic and antiangiogenic activities in vitro and in vivo. Recombinant TIMP-2 is currently undergoing preclinical testing in multiple, murine tumor models. Here we report the development of an inert, injectable peptide hydrogel matrix enabling encapsulation and sustained release of TIMP-2. We studied the TIMP-2 release profile from four β-hairpin peptide gels of varying net electrostatic charge. A negatively charged peptide gel (designated AcVES3) enabling encapsulation of 4 mg/mL of TIMP-2, without effects on rheological properties, facilitated the slow sustained release (0.9%/d) of TIMP-2 over 28 d. Released TIMP-2 is structurally intact and maintains the ability to inhibit MMP activity, as well as suppress lung cancer cell proliferation in vitro. These findings suggest that the AcVES3 hydrogel will be useful as an injectable vehicle for systemic delivery of TIMP-2 in vivo for ongoing preclinical development.

Humidity Influence on Optical Properties of Nanowire Colloids with Modulated Visual Response to Electrostatic Charge

Electric field created by the nearby electrostatic charge orients the colloidal nanowires in the medium of low dielectric constant, causing a visible color change. We show that the kinetics of subsequent color restoration correlates well to ambient relative humidity. Presented principle could be used for detecting humidity, which affects net surface electrostatic charge possibly via chemical reactions.

Antiproliferative activity of cobra venom cytotoxins.

Cytotoxins (or cardiotoxins, CTs) are small rigid membrane-active proteins of the three-finger toxin (TFT) family. They comprise about 60 amino acid residues, stabilized by four disulphide bridges. CTs, the most abundant proteins in cobra venom are able to kill cancer cells in a dose and time-dependent manner. The present review summarizes the current data on the molecular pathways of cancer cell death, induced by CTs. A relationship between structural characteristics of CTs and mechanism of their antiproliferative activity is reviewed as well. The CT molecules are rigid and their structure does not change significantly, when they interact with their molecular targets. This rigidity facilitates identification of molecular entities, responsible for antiproliferative activity of the toxins. We demonstrate that consideration of a net electrostatic charge and recently introduced HTL (Hydrophobicity of the Tips of the Loops) score allows distinguishing between the two mechanisms of cell death. The first is related to membrane destabilization by the toxins. The second involves their capture inside the cells, followed by interrogation into signal cascades mediated by the proteins, essential for cell life. Via addressing to antibacterial activity of CTs, which is supposed to arise from the plasma membrane damage, we demonstrate that, if membrane deterioration is involved in malignant cell death, the toxic activity of CTs correlates with their HTL scores and net electrostatic charge. We assume the relationship found may be used for rational design of antiproliferative compounds.

Electrocatalytic amplification of nanoparticle collisions at electrodes modified with polyelectrolyte multilayer films.

We report electrochemical catalytic amplification of individual collisions between ∼57 nm diameter Pt nanoparticles (Pt NPs) and 12.5 μm diameter Au ultramicroelectrodes modified with passivating, electrostatically assembled polyelectrolyte multilayer (PEM) films prepared by the layer-by-layer deposition method. Two key findings are reported. First, despite the thicknesses of the insulating PEM films, which range up to 5 nm, electrons are able to tunnel from the Pt NPs to the electrode resulting in electrocatalytic N2H4 oxidation at the PEM film-solution interface. These single-particle measurements are in accord with prior reports showing that the electrochemical activity of passive PEM films can be reactivated by adsorption of metallic NPs. Second, it is possible to control the frequency of the collisions by manipulating the net electrostatic charge present on the outer surface of the PEM thin film. These results, which demonstrate that chemistry can be used to control electrocatalytic amplification, set the stage for future sensing applications.

Parameters influencing the photo-induced electron transfer from tryptophan-containing peptides to a Ru(II) complex: a systematic study.

Ruthenium(II) polyazaaromatic complexes have gained interest in recent decades as biomolecular tools, especially in the development of new phototherapeutic agents. These light emissive Ru complexes based on π-deficient ligands were first designed to allow a photo-induced electron transfer (PET) with the guanine base in DNA since their (3)MLCT state is highly photo-oxidizing. Later the field of research was extended to proteins with the highlighting of a PET process with the tryptophan residue. This paper reports the kinetics of the luminescence quenching of [Ru(TAP)2phen](2+) by several selected peptide sequences containing at least one tryptophan residue. By using a peptide library we highlight the important parameters influencing the kinetics of the photo-electron transfer process, such as the net electrostatic charge and the number of tryptophan residues. The best peptide candidates were selected to study the formation of photo-products by MALDI-ToF mass spectrometry. A high photoreactivity of the [Ru(TAP)2phen](2+) complex was observed and multiple photoadducts were characterized, among them inter-peptidic adducts as well as intra-peptidic adducts.

Measurement of net electric charge and dipole moment of dust aggregates in a complex plasma.

Understanding the agglomeration of dust particles in complex plasmas requires knowledge of basic properties such as the net electrostatic charge and dipole moment of the dust. In this study, dust aggregates are formed from gold-coated mono-disperse spherical melamine-formaldehyde monomers in a radiofrequency (rf) argon discharge plasma. The behavior of observed dust aggregates is analyzed both by studying the particle trajectories and by employing computer models examining three-dimensional structures of aggregates and their interactions and rotations as induced by torques arising from their dipole moments. These allow the basic characteristics of the dust aggregates, such as the electrostatic charge and dipole moment, as well as the external electric field, to be determined. It is shown that the experimental results support the predicted values from computer models for aggregates in these environments.

Controlling the assembly of CdS nanorods via solvent and acidity.

We report control over the phase behavior of CdS nanorods via the solvent and acidity. CdS nanorods were synthesized using alkane phosphonic acid ligands, which were replaced after synthesis by a series of aromatic ligands. Change of ligand enabled us to cast films from different solvents. By replacing toluene with ethanol or water the rod-rod interactions dominate over rod-substrate interactions, thereby favoring simple hexagonal ordering (2D). When dispersed in water, a net electrostatic charge on the nanorods could be induced by deprotonating the ligands at high pH. This net charge favors 2D nematic ordering over homeotropic ordering of the nanorods on a substrate. A calculation of the van der Waals and electrostatic interactions is presented that explains the observed influence of solvent and pH.

Polymer coating of carrier excipients modify aerosol performance of adhered drugs used in dry powder inhalation therapy

The potential of excipient coating to enhance aerosol performance of micronized drugs in carrier excipient-drug blends, used in dry powder inhalers, was investigated. Both EC (ethyl cellulose) and PVP (polyvinylpyrrolidone) were used as coating agents. Carriers were prepared via sieve fractioning followed by spray drying, with and without polymer additive. Each uncoated and coated carrier salbutamol sulphate (SS) blended systems were evaluated for particle size, morphology, drug carrier adhesion and aerosolisation performance, after blending and storage for 24h. All carrier-based systems prepared had similar particle sizes and morphologies. The surface chemistries of the carriers were significantly different, as was drug-carrier adhesion and aerosolisation performance. Particle adhesion between SS and aerosol performance (fine particle fraction; FPF) followed the rank: PVP coated>un-coated>EC coated lactose. This rank order could be attributed to the surface energy measured by contact goniometry and related to the chemistry of lactose and each polymer. Storage did not significantly affect aerosol performance, however a rank increase in mean FPF value was observed for uncoated and EC coated lactose. Finally, the net electrostatic charge across the aerosol cloud indicated that the EC coated lactose transferred less charge to SS particles. The performance of each carrier system could be attributed to the carrier surface chemistry and, in general, by careful selection of the coating polymer, drug-carrier adhesion, electrostatic charge and aerosol performance could be controlled.

Actuation to sensing crosstalk investigation in the inertial sensor front-end electronics of the laser interferometer space antenna pathfinder satellite

Abstract The inertial sensor (IS) front-end electronic (FEE) is considered to be one of the most critical designs in the laser interferometer space antenna (LISA) and LISA pathfinder (LPF) satellite. The actuation to sensing crosstalk in the IS FEE could deteriorate the IS test mass (TM) sensing information, thus affect the TM control and the mission performance critical estimation of the TM net electrostatic charge level. By detailed modeling, we find that the crosstalk is most likely caused by the capacitance variation at the output stage of the actuation circuit due to the applied actuation signal. Different types of capacitors were tested in the prototype sensing and actuation circuit and the sensing performance for different actuation signals were measured. The measurement results show that the crosstalk in our prototype circuit can be made negligible, but not fully avoided since the capacitors are not absolutely constant when the actuation signal is applied. Compared to the use of other types of capacitors, the use of polyphenylene sulphide (PPS), polyester (PET) and C0G type capacitors can achieve better performance with crosstalk level far below the limit.

Investigations into the molecular-level adhesion characteristics of hydroxyapatite-coated and anodized titanium surfaces using the molecular orbital approach.

It has been established that the adhesion of cells on to the surfaces of orthopaedic implants depends on the ability of the surfaces to accommodate protein molecules. Hydroxyapatite coating and anodizing are the most common methods to make TiAl6V4 implants (Ti) more biocompatible. In this paper Spartan 02, a molecular dynamics software, is used to analyze and predict the bonding characteristics of Extra cellular matrix protein sequence arginine-glycine-aspartic acid (RGD) on a Hyrdoxyapatite (HA) coated Ti and an anodized Ti surface based on the property of its constituent atoms, their polarity (net electrostatic charge, Qr), the energies of the molecular orbital E_HOMO (energy of the highest occupied molecular orbital), and E_LUMO (energy of the lowest unoccupied molecular orbital). The results show favourable criterion for formation of bonding between the HOMO orbital of the HA coated and anodized surfaces and LUMO orbital of the glycine strand from the RGD unit. The mechanism of bonding of individual atoms to form primary calcium oxide compounds is likely only in the case of HA coated surfaces . The surface texture of the anodized Ti with inherent porosities appear more responsible for the adsorption of proteins on to them by mechanical interlocking than the formation of any intermediate calcium oxide compounds.