Direct electrochemistry and electrocatalysis of hemoglobin based on poly(diallyldimethylammonium chloride) functionalized graphene sheets/room temperature ionic liquid composite film

The functionalized graphene nanosheets (PDDA-G) with poly(diallyldimethylammonium chloride) (PDDA) were synthesized and used to combine with room temperature ionic liquid (RTIL). The resulting RTIL/PDDA-G composite displayed an enhanced capability for the immobilization of hemoglobin to realize its direct electrochemistry. Moreover, the RTIL/PDDA-G based biosensor exhibited excellent electrocatalytic activity for the detection of nitrate with a wide linear range from 0.2 to 32.6 μM and a low detection limit of 0.04 μM at 3σ. This work opens a new way to functionalized graphene nanosheets with good biocompatibility and solubility in biosensors.     

Simultaneous determination of catechol and hydroquinone based on poly (diallyldimethylammonium chloride) functionalized graphene-modified glassy carbon electrode

Simultaneous determination of catechol (CC) and hydroquinone (HQ) were investigated by voltammetry based on glassy carbon electrode (GCE) modified by poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene (PDDA-G). The modified electrode showed excellent sensitivity and selectivity properties for the two dihydroxybenzene isomers. In 0.1 mol/L phosphate buffer solution (PBS, pH 7.0), the oxidation peak potential difference between CC and HQ was 108 mV, and the peaks on the PDDA-G/GCE were three times as high as the ones on graphene-modified glass carbon electrode. Under optimized conditions, the PDDA-G/GCE showed wide linear behaviors in the range of 1 × 10⁻⁶−4 × 10⁻⁴ mol/L for CC and 1 × 10⁻⁶−5 × 10⁻⁴ mol/L for HQ, with the detection limits 2.0 × 10⁻⁷ mol/L for CC and 2.5 × 10⁻⁷ mol/L for HQ (S/N = 3) in mixture, respectively. Some kinetic parameters, such as the electron transfer number (n), charge transfer coefficient (α), and the apparent heterogeneous electron transfer rate constant (k _s), were calculated. The proposed method was applied to simultaneous determine CC and HQ in real water samples of Yellow River with satisfactory results.     

Enhanced oxygen reduction at Pd catalytic nanoparticles dispersed onto heteropolytungstate-assembled poly(diallyldimethylammonium)-functionalized carbon nanotubes

Both Keggin-type phosphotungstic acid (HPW) and Pd are not prominent catalysts towards the oxygen reduction (ORR), but their composite Pd-HPW catalyst produces a significantly higher electrochemical activity for the ORR in acidic media. The novel composite catalyst was synthesized by self-assembly of HPW on multi-walled carbon nanotubes (MWCNTs) via the electrostatic attraction between negatively charged HPW and positively charged poly(diallyldimethylammonium (PDDA)-wrapped MWCNTs, followed by dispersion of Pd nanoparticles onto the HPW-PDDA-MWCNT assembly. The as-prepared catalyst was characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). TEM images show that Pd nanoparticles were uniformly dispersed on the surface of MWCNTs even when the Pd loading was increased to 60 wt%. Electrochemical activity of the catalysts for the ORR was evaluated by steady state polarization measurements using a rotating disk electrode. Compared with the acid treated MWCNTs, Pd nanoparticles supported on the HPW-assembled MWCNTs show a much higher ORR activity that is comparable to conventional Pt/C catalysts. The high electrocatalytic activities could be related to high dispersion of Pd nanoparticles as well as synergistic effects originating from the high proton conductivity of HPW. The Pd/HPW-PDDA-MWCNTs system as the cathode catalyst in proton exchange membrane fuel cells is demonstrated.     

Ultradisperse catalytic layers supported by nanotubes and poly(diallyldimethylammonium)chloride polymer

A catalytic system consisting of carbon nanotubes, poly(diallyldimethylammonium)chloride, and a very thin layer of platinum or platinum-ruthenium is assembled layer-by-layer (LbL) on a glassy carbon (GC) electrode. Deposits of platinum metals are studied by electrochemical methods, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). Such catalyst layers are shown to exhibit much higher activity in the methanol oxidation reaction as compared with commercial and electroplated catalysts. The currents compared are calculated per the surface area of deposited metals determined with respect to hydrogen adsorption.     

Investigation of thermophysical properties of nanofluids containing poly(vinyl alcohol)-functionalized graphene

An experimental study was performed to evaluate the colloidal stability of water-based polyvinyl alcohol-functionalized few-layer graphene (water-based PVA–Gr) nanofluids and ethylene glycol-based polyvinyl alcohol-functionalized few-layer graphene (EG-based PVA–Gr) nanofluids. To this end, a liquid-phase exfoliation method was employed for mass production of graphene sheets (Gr). Then, a simple and novel method was introduced to do a direct functionalization of Gr with PVA. Surface functionality groups and morphology of PVA–Gr were analyzed by infrared spectroscopy, Raman spectroscopy and transmission electron microscopy. The results consistently confirmed the formation of PVA functionalities on Gr, while the structure of GNP has remained relatively intact. Then, UV–Vis was employed to investigate the stability of PVA–Gr in water and EG. The easily miscible PVA functionalities formed a great colloidal stability for Gr sheets. As a second criterion for having a promising coolant, thermophysical properties were measured experimentally. The thermal conductivity, density and viscosity of the nanofluids at concentrations of 0.025, 0.05 and 0.1 mass% were experimentally measured. As compared to the base fluid, the water-based PVA–Gr nanofluids show a significant enhancement at different conditions, like representing ~40% enhancement for 0.1 mass% at 40 °C. This simple and efficient procedure may play an important role for mass production of hydrophilic Gr, which be able to disperse in different solvents.     

Colloid stability of sodium dihexadecyl phosphate/poly(diallyldimethylammonium chloride) decorated latex

The colloid stability of supramolecular assemblies composed of the synthetic anionic lipid sodium dihexadecyl phosphate (DHP) on cationic poly(diallyldimethylammonium chloride) (PDDA) supported on polystyrene sulfate (PSS) microspheres was evaluated via turbidimetry kinetics, dynamic light scattering for particle sizing, zeta-potential analysis, and determination of DHP adsorption on PDDA-covered particles. At 0.05 g/L PDDA and 5 x 10(9) PSS particles/mL, PDDA did not induce significant particle flocculation and a vast majority of PDDA covered single particles were present in the dispersion so that this was the condition chosen for determining DHP concentration (C) effects on particle size and zeta-potentials. At 0.8 mM DHP, charge neutralization, maximal size, and visible precipitation indicated extensive flocculation and minimal colloid stability for the DHP/PDDA/PSS assembly. At 0.05 g L(-1) PDDA, isotherms of high affinity for DHP adsorption on PDDA-covered particles presented a plateau at a limiting adsorption of 135 x 10(19) DHP molecules adsorbed per square meter PSS which was well above bilayer deposition on a smooth particle surface. The polyelectrolyte layer on hydrophobic particles was swelled and fluffy yielding ca. 6 +/- 1.5 nm hydrodynamic thickness. Maximal and massive adsorption of DHP lipid onto this layer produced polydisperse DHP/PDDA/PSS colloidal particles with low colloid stability and which, at best, remained aggregated as doublets over a range of large lipid concentrations so that it was not possible to evaluate the mean total thickness for the deposited film. The assembly anionic lipid/cationic PDDA layer/polymeric particle was relatively stable as particle doublets only well above charge neutralization of the polyelectrolyte by the anionic lipid, at relatively large lipid concentrations (above 1 mM DHP) with charge neutralization leading to extensive particle aggregation.     

Modification of superparamagnetic iron oxide nanoparticles with poly(diallyldimethylammonium chloride) at air atmosphere

Superparamagnetic iron oxide particles with average size less than 20 nm were prepared by chemical co‐precipitation method in the air atmosphere. After that, polydimethyldiallyl ammonium chloride (PDDA) was used for wrapping iron oxide particles to obtain the core/shell nanocomposites. The parameters influencing properties of iron oxide particles and iron oxide/PDDA nanocomposites were investigated and optimized. The prepared iron oxide and nanocomposites were characterized by X‐ray diffraction (XRD) measurement, transmission electron microscopy (TEM), particle size and Zeta potential analyzer, Fourier transform infrared (FTIR) spectroscopy, and vibrating sample magnetometry (VSM), respectively. It was found that the iron oxide particles are cubic inverse spinel Fe₃O₄ with spherical shape. Superparamagnetic behavior of Fe₃O₄ with 73.114 emu/g is produced with NH₄OH as precipitator, and decreased to 58.583 emu/g for Fe₃O₄/PDDA nanocomposites. The Zeta potential of nanocomposites is positive value. The results showed that Fe₃O₄/PDDA nanocomposites have excellent future using as a carrier for bonding with some negative charged particles. Copyright © 2016 John Wiley & Sons, Ltd.     

Polyelectrolyte complexation between poly(methacrylic acid,sodium salt) and poly(diallyldimethylammonium chloride) or poly[2‐(methacryloyloxyethyl) trimethylammonium chloride]

Polyelectrolyte complexes between poly(methacrylic acid, sodium salt) and poly(diallyldimethylammonium chloride) (PDADMAC) or poly[2‐(methacryloyloxyethyl)trimethylammonium chloride] (PMOETAC) form gels, liquid phases, or soluble complexes depending on charge ratio, total polymer loading, polymer molecular weight, and ionic strength. Increasing the ionic strength of the medium led most polyelectrolyte pairs to transition from gel through liquid complexes (complex coacervate) to soluble complexes. These transitions shift to higher ionic strengths for higher molecular weight polymers, as well as for PMOETAC compared to PDADMAC. The complex phases swelled with increasing polymer loading, ultimately merging with the supernatant phase at a critical polymer loading. The isolated liquid complex phases below and above this critical loading were temperature‐sensitive, showing cloud points followed by macroscopic phase separation upon heating. Incorporating 5 mol % lauryl methacrylate into the polyanion led to increased complex yield with PDADMAC, and increased resistance to ionic strength. In contrast, incorporating 30 mol % of oligo(ethylene glycol) methacrylate into the polyanion led to decreased complex yield, and to lower resistance to ionic strength. Two polyelectrolyte systems that produced liquid complexes were used to encapsulate hydrophobic oils, and in one case were used to demonstrate the feasibility of crosslinking the resulting capsule walls. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4129–4143, 2007     

聚二甲基二烯丙基氯化铵及其与CTAB混合物水溶液 的吸附动力学

用最大泡压法分别测定了聚二甲基二烯丙基氯化铵,十六烷基三甲基溴化铵以及两者混合物水溶液的动表面张力。十六烷基三甲基溴化铵的吸附服从扩散-动力学控制机理。发现聚二甲基二烯丙基氯化铵水溶液的表面张力具有独特的时间相关性。吸附的前期服从扩散控制机理,而在吸附的后期,即接近吸附平衡时服从扩散-动力学控制机理。混合物水溶液的整个吸附过程受扩散控制。     

Polymer-surfactant interactions: binding mechanism of sodium dodecyl sulfate to poly(diallyldimethylammonium chloride)

The binding mechanism of poly(diallyldimethylammonium chloride), PDAC, and sodium dodecyl sulfate, SDS, has been comprehensively studied by combining binding isotherms data with microcalorimetry, zeta potential, and conductivity measurements, as well as ab initio quantum mechanical calculations. The obtained results demonstrate that surfactant-polymer interaction is governed by both electrostatic and hydrophobic interactions, and is cooperative in the presence of salt. This binding results in the formation of nanoparticles, which are positively or negatively charged depending on the molar ratio of surfactant to PDAC monomeric units. From microcalorimetry data it was concluded that the exothermic character of the interaction diminishes with the increase in the surfactant/polymer ratio as well as with an increase in electrolyte concentration.     

Preparation of solid alkaline fuel cell binders based on fluorinated poly(diallyldimethylammonium chloride)s [poly(DADMAC)] or poly(chlorotrifluoroethylene‐co‐DADMAC) copolymers

A membrane or an electrode binder to be used in a solid alkaline fuel cell (SAFC) needs to (i) be insoluble in both aqueous solutions and the required fuels, and (ii) exhibit an hydroxide ion conductivity. To achieve these goals, two pathways were employed: (i) one consists of the radical copolymerization of diallyldimethylammonium chloride (DADMAC) with chlorotrifluoroethylene (CTFE) while (ii) the other one is based on the counter‐ion exchange of a poly(DADMAC) by fluorinated anions. First, the radical copolymerization of CTFE with DADMAC under various experimental conditions was achieved in yields up to 85%, and DADMAC percentages in the copolymers were higher than those in the feed compositions. To obtain insoluble copolymers, high CTFE feed contents (>70 mol %) were required. The other route consisting in the partial replacement of the Cl^? counter‐ions in the water‐soluble poly(DADMAC) by bistrifluoromethanesulfonimide (TFSI^?) did confer the starting material insolubility in water while maintaining its conductivity. When the fluorinated poly(DADMAC) was obtained from concentrated solutions of fluorinated surfactant, it was observed that the amount of counter‐ions exchanged was difficult to control, which limits optimization. Nevertheless, under diluted conditions, membranes with ion exchange capacity up to 0.7 meq g^?1, and conductivities close to 1 mS cm^?1 were obtained. Although their conductivities were low, these membranes fulfill the requirements for a SAFC membrane in terms of solubility in DMSO, water insolubility, and thermal stability (T_d,10% > 320 °C). When used in a fuel cell, as a binder in the membrane‐electrode assembly (MEA), significant improvements were noted (+50% of the open circuit voltage, +580% in current density, and +540% in accessible power). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2043–2058, 2009     

Poly(indole-5-carboxylic acid)-functionalized ZnO nanocomposite for electrochemical DNA hybridization detection

Journal of Solid State Electrochemistry - In this paper, a novel direct DNA electrochemical biosensor was developed for detection of breakpoint cluster region gene and the cellular abl (BCR/ABL)...     

碳纳米管/聚二烯丙基二甲基氯化铵/磷钼酸复合膜的组装及其在溴酸盐检测中的应用

通过静电层层组装技术在玻碳(GC)电极表面制备{多壁碳纳米管(MWCNT)/聚二烯丙基二甲基氯化铵(PDDA)}n多层膜,并采用循环伏安法在多层膜的表面电化学修饰一层磷钼酸(PMo12)膜,构筑GC/{MWCNT/PDDA}n-PMo12复合膜修饰电极.利用SEM对比观察{MWCNT/PDDA}n和{PDDA/MWCNT}n-PMo12的微观结构,并研究该复合膜修饰电极的电化学及其对溴酸盐(BrO3-)电催化还原性质.在此基础上研发一种基于GC/{MWCNT/PDDA}n-PMo12复合膜修饰电极的电流型BrO3-传感器,该传感器表现出明显增大的响应电流.在最优的实验条件下,采用电流时间曲线(i-t)法考察该复合膜修饰电极对BrO3-的安培响应.实验结果表明,该传感器在BrO3-浓度为50～400nmol/L的范围内具有良好的线性关系,相关系数R2为0.9950,响应时间为1.53s,检出限为20nmol/L,灵敏度为13.81mA(mmol/L)-1cm-2.     

A novel immunosensor for carcinoembryonic antigen based on poly(diallyldimethylammonium chloride) protected prussian blue nanoparticles and double-layer nanometer-sized gold particles

A highly sensitive amperometric immunosensor has been developed for the detection of carcinoembryonic antigen (CEA). It is based on (a) Prussian Blue nanoparticles coated with poly(diallyldimethylammonium chloride) (P-PB) and (b) double-layer gold nanocrystals. The sensor was obtained by first electrodepositing porous gold nanocrystals on the glassy carbon electrode (GCE), and then by modifying the electrode with the coated P-PB. Subsequently, colloidal gold nanoparticles (nano-Au) were adsorbed onto the GCE by electrostatic interactions between the negatively charged nano-Au and the positively charged P-PB to immobilize CEA antibodies. Finally, bovine serum albumin was employed to block possible remaining active sites and to prevent the non-specific adsorption on the nano-Au. This immunosensor was characterized by cyclic voltammetry and scanning electron microscopy. The working range was adjusted to two concentration ranges, viz. from 0.5 to 10 ng.mL^?1, and from 10 to 120 ng.mL^?1 of CEA, with a detection limit of 0.2 ng.mL^?1 at three times the background noise.     

Sensitive detection of biomolecules and DNA bases based on graphene nanosheets

High surface area electrode materials are of interest for the application of electrochemical sensors. Currently, chemical vapor deposition (CVD) graphene-sensing electrodes are scarce. Herein, for the first time, a graphene based on a Ta wire support was prepared using the CVD method to form a highly electroactive biosensing platform. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse voltammetry (DPV) were utilized to characterize the morphology and investigate the electrochemical properties of the CVD graphene electrodes. The resulting CVD graphene electrode exhibited good electrocatalytic activity and had a prominent response effect on dopamine, uric acid, guanine, and adenine. Standing graphene nanosheets have rich catalytic sites such as the edges, the defect levels of the plane, and porous network structures between the graphene nanosheets. These catalytic sites prompt the adsorption and resolution for the four species and the strong electron transport capability of the CVD graphene, which effectively improved the electrical signals for response to four species. Moreover, the graphene electrode is a promising candidate in electrochemical sensing and other electrochemical device applications.     

Thermoelectric properties of nanocomposite thin films prepared with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) and graphene

Carbon nanotubes (CNTs), either single wall carbon nanotubes (SWNTs) or multiwall carbon nanotubes (MWNTs), can improve the thermoelectric properties of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT?:?PSS), but it requires addition of 30-40 wt% CNTs. We report that the figure of merit (ZT) value of PEDOT?:?PSS thin film for thermoelectric property is increased about 10 times by incorporating 2 wt% of graphene. PEDOT?:?PSS thin films containing 1, 2, 3 wt% graphene are prepared by solution spin coating method. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses identified the strong π-π interactions which facilitated the dispersion between graphene and PEDOT?:?PSS. The uniformly distributed graphene increased the interfacial area by 2-10 times as compared with CNT based on the same weight. The power factor and ZT value of PEDOT?:?PSS thin film containing 2 wt% graphene was 11.09 μW mK(-2) and 2.1 × 10(-2), respectively. This enhancement arises from the facilitated carrier transfer between PEDOT?:?PSS and graphene as well as the high electron mobility of graphene (200,000 cm(2) V(-1) s(-1)). Furthermore the porous structure of the thin film decreases the thermal conductivity resulting in a high ZT value, which is higher by 20% than that for a PEDOT?:?PSS thin film containing 35 wt% SWNTs.     

A conductivity study and calorimetric analysis of dried poly(sodium 4-styrene sulfonate)/poly(diallyldimethylammonium chloride) polyelectrolyte complexes

Ionically cross-linked polyelectrolyte complexes (PECs) of anionic poly(sodium 4-styrene sulfonate) (PSS) and cationic poly(diallyldimethylammonium chloride) (PDADMAC), xPSS.(1-x)PDADMAC, with molar fractions x ranging from 0.30 to 0.70, were prepared and subsequently dried. The PEC samples were analyzed by differential scanning calorimetry, and the ionic conductivity sigmadc of the samples was measured as a function of temperature by means of impedance spectroscopy. The thermograms display an endothermic peak in the temperature range of 90-143 degrees C, which is attributed to a glass transition of the PEC. The glass transition temperature Tg has a symmetric x dependence with a minimum at x=0.50. The temperature dependence of sigmadcT is not affected by the glass transition. The ionic conductivity of the samples before drying is three orders of magnitude larger than sigmadc after drying; nevertheless, their activation enthalpies are identical. Arrhenius parameters obtained from the systematic study of several PEC compositions are discussed. The ionic conductivity of the PSS-rich samples is significantly higher than sigmadc of PDADMAC-rich samples. This implies a relatively high Na+ mobility as compared to Cl(-) mobility in PEC. In contrast to the symmetric x dependence of Tg, the conductivity of PEC increases and the activation enthalpy decreases with increasing x in the investigated composition range. A strong x dependence of sigmadc is observed for PSS-rich PEC, which is attributed to a significant variation in the mobility of the charge carriers.     

Electrically conducting,transparent, graphene based nanocomposite coatings on flexible film substrate

Transparent, electrically conducting nanocomposite coated polyethylene terephthalate (PET) films are prepared using two types of bulk synthesized few layered graphene; namely reduced graphene oxide (rGO) and liquid exfoliated graphite (EG) dispersed in ultra high molecular weight polyethylene (UHMWPE). This study focuses on application of high concentration of such nanofillers (1: 1 to 2.5: 1 ratios with polymer) in order to develop a highly conducting but ultrathin coating for better transparency. The coated PET films are characterized for their surface morphology, electrical and optical properties. High resolution transmission electron microscopic (HRTEM) images and corresponding selected area electron diffraction (SAED) patterns confirm that the graphite has been exfoliated to few layer graphene using both the synthesis routes. Transmittance values of these coated films are measured in UV visible spectrum. The rGO based samples have high transmittance (~90–95%) compared to EG based samples (~40–50%). From current-voltage (I?V) graph and surface resistivity studies, it has been observed that rGO based samples are dielectric in nature similar to UHMWPE while EG based samples are electrically conducting and its conductivity increases with its concentration. EG based nanocomposite coated samples show much better electrical conductivities (resistance 338 to 66 kΩ at different concentrations of EG) than rGO based samples.     

Modulating the structure and properties of poly(sodium 4-styrenesulfonate)/poly(diallyldimethylammonium chloride) multilayers with concentrated salt solutions

Poly(sodium 4-styrenesulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) multilayers were treated with 1-5 M NaCl solutions, resulting in continuous changes in the physicochemical properties of the multilayers. Significant mass loss was observed when the salt concentration was higher than 2 M and reached as high as 72% in a 5 M NaCl solution. The disassembly occurred initially in the superficial layers and then developed in the bulk multilayers. For the multilayers with PDADMAC as the outmost layer, the molar ratio of PSS/PDADMAC was increased and the surface chemistry was changed from PDADMAC domination below 2 M NaCl to PSS domination above 3 M NaCl. Owing to the higher concentrations of uncompensated for polyelectrolytes at both lower and higher salt concentrations, the swelling ratio of the multilayers was decreased until reaching 3 M NaCl and then was increased significantly again. The salt-treated PSS/PDADMAC thin films are expected to show different behaviors in terms of the physical adsorption of various functional substances, cell adhesion and proliferation, and chemical reaction activity.     

Potential driven deposition of poly(diallyldimethylammonium chloride) onto the surface of 3-mercaptopropionic acid monolayers assembled on gold

Electrochemical impedance spectroscopy (EIS) and quartz crystal microbalance (QCM) measurements are used to examine the ability of applied potential to drive the ionic self-assembly of poly(diallyldimethylammonium) chloride (PDDA) onto a substrate modified with a monolayer of 3-mercaptopropionic acid (3-MPA). The potential of zero charge (PZC) of the gold electrode modified with a monolayer of 3-MPA was found by differential capacitance measurements to be -0.12 (+/-0.01) V versus Ag-AgCl. Changing the substrate potential to values positive (-0.01 V vs Ag-AgCl) of the PZC induces interfacial conditions that are favorable for the electrostatic deposition of cationic polymers onto the surface of 3-MPA monolayers. This result is also consistent with experimental observations obtained when the 3-MPA-modified substrate is exposed to 0.10 mol L (-1) NaOH solutions. When potentials equal or negative to the PZC are applied to the substrate, no significant accumulation of the PDDA is found by either QCM or EIS measurement. This result is consistent with results obtained when the 3-MPA modified substrate is exposed to 0.10 mol L (-1) HCl solutions where no PDDA adsorption is expected because the monolayer is neutral under these conditions. Changes in the impedance and quartz crystal frequency obtained after potential is applied to the substrate are interpreted in terms of the applied potential creating interfacial conditions that are favorable for the deprotonation of the terminal carboxylic acid groups and the subsequent electrostatic assembly of the polycation onto the negatively charged monolayer.