Molecular Weights of Polyethyleneimine-Dependent Physicochemical Tuning of Gold Nanoparticles and FRET-Based Turn-On Sensing of Polymyxin B.

Environmental monitoring and the detection of antibiotic contaminants require expensive and time-consuming techniques. To overcome these challenges, gold nanoparticle-mediated fluorometric "turn-on" detection of Polymyxin B (PMB) in an aqueous medium was undertaken. The molecular weight of polyethyleneimine (PEI)-dependent physicochemical tuning of gold nanoparticles (PEI@AuNPs) was achieved and employed for the same. The three variable molecular weights of branched polyethyleneimine (MW 750, 60, and 1.3 kDa) molecules controlled the nano-geometry of the gold nanoparticles along with enhanced stabilization at room temperature. The synthesized gold nanoparticles were characterized through various advanced techniques. The results revealed that polyethyleneimine-stabilized gold nanoparticles (PEI@AuNP-1-3) were 4.5, 7.0, and 52.5 nm in size with spherical shapes, and the zeta potential values were 29.9, 22.5, and 16.6 mV, respectively. Accordingly, the PEI@AuNPs probes demonstrated high sensitivity and selectivity, with a linear relationship curve over a concentration range of 1-6 µM for polymyxin B. The limit of detection (LOD) was calculated as 8.5 nM. This is the first unique report of gold nanoparticle nano-geometry-dependent FRET-based turn-on detection of PMB in an aqueous medium. We believe that this approach would offer a complementary strategy for the development of a highly sophisticated and advanced sensing system for PMB and act as a template for the development of new nanomaterial-based engineered sensors for rapid antibiotic detection in environmental as well as biological samples.

Aggregation-Resistant, Turn-On-Off Fluorometric Sensing of Glutathione and Nickel (II) Using Vancomycin-Conjugated Gold Nanoparticles.

Glutathione (GSH) and nickel (II) cation have an indispensable role in various physiological processes, including preventing the oxidative damage of cells and acting as a cofactor for lipid metabolic enzymes. An imbalance in the physiological level of these species may cause serious health complications. Therefore, sensitive and selective fluorescent probes for the detection of GSH and nickel (II) are of great interest for clinical as well as environmental monitoring. Herein, vancomycin-conjugated gold nanoparticles (PEI-AuNP@Van) were prepared and employed for the detection of GSH and nickel (II) based on a turn-on-off mechanism. The as-synthesized PEI-AuNP@Van was ~7.5 nm in size; it exhibited a spherical shape with face-centered cubic lattice symmetry. As compared to vancomycin unconjugated gold nanoparticles, GSH led to the turn-on state of PEI-AuNP@Van, while Ni2+ acted as a fluorescence quencher (turn-off) without the aggregation of nanoparticles. These phenomena strongly justify the active role of vancomycin conjugation for the detection of GSH and Ni2+. The turn-on-off kinetics was linearly proportional over the concentration range between 0.05-0.8 µM and 0.05-6.4 µM. The detection limits were 205.9 and 90.5 nM for GSH and Ni2+, respectively; these results are excellent in comparison to previous reports. This study demonstrates the active role of vancomycin conjugation for sensing of GSH and Ni2+ along with PEI-AuNP@Van as a promising nanoprobe.

Synthesis of vancomycin functionalized fluorescent gold nanoparticles and selective sensing of mercury (II).

Mercury ions (Hg2+) are widely found in the environment; it is considered a major pollutant. Therefore, the rapid and reliable detection of Hg2+ is of great technical interest. In this study, a highly fluorescent, sensitive, and selective fluorometric assay for detecting Hg2+ ions was developed using vancomycin functionalized and polyethyleneimine stabilized gold nanoparticles (PEI-f-AuNPs@Van). The as-made gold nanoparticles were highly fluorescent, with excitation and emission maxima occurring at 320 and 418 nm, respectively. The size of nanoparticles was ~7 nm; a zeta potential of ~38.8 mV was determined. The XRD analysis confirmed that the nanoparticles possessed crystalline structure with face centerd cubic symmetry. Using the PEI-f-AuNP@Van probe, the detection limit of Hg2+ ion was achieved up to 0.988 nM (within a linear range) by calculating the KSV. However, the detection limit in a natural environmental sample was shown to be 12.5 nM. Furthermore, the selectivity tests confirmed that the designed probe was highly selective to mercury (II) cations among tested other divalent cations. Owing to its sensitivity and selectivity, this approach for Hg2+ ions detection can be utilized for the analysis of real water samples.

A whole cell fluorescence quenching-based approach for the investigation of polyethyleneimine functionalized silver nanoparticles interaction with Candida albicans.

The antimicrobial activity of metal nanoparticles can be considered a two-step process. In the first step, nanoparticles interact with the cell surface; the second step involves the implementation of the microbicidal processes. Silver nanoparticles have been widely explored for their antimicrobial activity against many pathogens. The interaction dynamics of functionalized silver nanoparticles at the biological interface must be better understood to develop surface-tuned biocompatible nanomaterial-containing formulations with selective antimicrobial activity. Herein, this study used the intrinsic fluorescence of whole C. albicans cells as a molecular probe to understand the cell surface interaction dynamics of polyethyleneimine-functionalized silver nanoparticles and antifungal mechanism of the same. The results demonstrated that synthesized PEI-f-Ag-NPs were ~ 5.6 ± 1.2 nm in size and exhibited a crystalline structure. Furthermore, the recorded zeta potential (+18.2 mV) was associated with the stability of NPS and shown a strong electrostatic interaction tendency between the negatively charged cell surface. Thus, rapid killing kinetics was observed, with a remarkably low MIC value of 5 µg/mL. PEI-f-Ag-NPs quenched the intrinsic fluorescence of C. albicans cells with increasing incubation time and concentration and have shown saturation effect within 120 min. The calculated binding constant (Kb = 1 × 105 M-1, n = 1.01) indicated strong binding tendency of PEI-f-Ag-NPs with C. albicans surface. It should also be noted that the silver nanoparticles interacted more selectively with the tyrosine-rich proteins in the fungal cell. However, calcofluor white fluorescence quenching showed non-specific binding on the cell surface. Thus, the antifungal mechanisms of PEI-f-Ag-NPs were observed as reactive oxygen species (ROS) overproduction and cell wall pit formation. This study demonstrated the utility of fluorescence spectroscopy for qualitative analysis of polyethyleneimine-functionalized silver nanoparticle interaction/binding with C. albicans cell surface biomolecules. Although, a quantitative approach is needed to better understand the interaction dynamics in order to formulate selective surface tuned nanoparticle for selective antifungal activity.

Properties, Applications and Toxicities of Organotrialkoxysilane-Derived Functional Metal Nanoparticles and Their Multimetallic Analogues.

Sol-gel chemistry offers a very unique tool for nanoscale mastering of material preparation from metal alkoxides [...].

Size and Zeta Potential Clicked Germination Attenuation and Anti-Sporangiospores Activity of PEI-Functionalized Silver Nanoparticles against COVID-19 Associated Mucorales (Rhizopus arrhizus).

The SARS-CoV-2 infections in Indian people have been associated with a mucormycotic fungal infection caused by the filamentous fungi Rhizopus arrhizus. The sporangiospores of R. arrhizus are omnipresent in the environment and cause infection through inhalation or ingestion of contaminated air and foods. Therefore, the anti-sporangiospore activity of polyethyleneimine functionalized silver nanoparticles (PEI-f-Ag-NPs) with variable size and surface charge as a function of the molecular weight of PEI was explored. The results showed that both PEI-f-AgNP-1 and PEI-f-AgNP-2, potentially, attenuated the germination and reduced the viability of sporangiospores. Furthermore, the results showed that the minimum inhibitory concentration (MIC) values of both PEI-f-AgNP-1 and PEI-f-AgNP-2 (1.65 and 6.50 µg/mL, respectively) were dependent on the nanoparticle size and surface ζ potentials. Similarly, the sporangiospore germination inhibition at MIC values was recorded, showing 97.33% and 94% germination inhibition, respectively, by PEI-f-AgNP-1 and 2 within 24 h, respectively. The confocal laser scanning microscopy, SEM-EDS, and confocal Raman spectroscopy investigation of PEI-f-Ag-NPs treated sporangiospores confirmed size and surface charge-dependent killing dynamics in sporangiospores. To the best of our knowledge, this is the first investigation of the polyethyleneimine functionalized silver nanoparticle-mediated size and surface charge-dependent anti-sporangiospore activity against R. arrhizus, along with a possible antifungal mechanism.

Nanotechnology: A Potential Weapon to Fight against COVID-19.

The COVID-19 infections have posed an unprecedented global health emergency, with nearly three million deaths to date, and have caused substantial economic loss globally. Hence, an urgent exploration of effective and safe diagnostic/therapeutic approaches for minimizing the threat of this highly pathogenic coronavirus infection is needed. As an alternative to conventional diagnosis and antiviral agents, nanomaterials have a great potential to cope with the current or even future health emergency situation with a wide range of applications. Fundamentally, nanomaterials are physically and chemically tunable and can be employed for the next generation nanomaterial-based detection of viral antigens and host antibodies in body fluids as antiviral agents, nanovaccine, suppressant of cytokine storm, nanocarrier for efficient delivery of antiviral drugs at infection site or inside the host cells, and can also be a significant tool for better understanding of the gut microbiome and SARS-CoV-2 interaction. The applicability of nanomaterial-based therapeutic options to cope with the current and possible future pandemic is discussed here.

Amine-Functionalized Silver Nanoparticles: A Potential Antiviral-Coating Material with Trap and Kill Efficiency to Combat Viral Dissemination (COVID-19).

The outbreak of COVID-19 has drastically affected the daily lifestyles of people globally where specific Coronavirus-2 transmits primarily by respiratory droplets. Structurally, the SARS-CoV-2 virus is made up of four types of proteins in which S-protein is indispensable among them, as it causes rapid replication in the host body. Therefore, the glycine and alanine composed of HR1 of S-protein is the ideal target for antiviral action. Different forms of surface-active PPEs can efficiently prevent this transmission in this circumstance. However, the virus can survive on the conventional PPEs for a long time. Hence, the nanotechnological approaches based on engineered nanomaterials coating on medical equipments can potentially prevent the dissemination of infections in public. Silver nanoparticles with tuneable physicochemical properties and versatile chemical functionalization provide an excellent platform to combat the disease. The coating of amine-functionalized silver nanoparticle (especially amine linked to aliphatic chain and trialkoxysilane) in its nanostructured form enables cloths trap and kill efficient. PPEs are a primary and reliable preventive measure, although they are not 100% effective against viral infections. So, developing and commercializing surface-active PPEs with trap and kill efficacy is highly needed to cope with current and future viral infections. This review article discusses the COVID-19 morphology, antiviral mechanism of Ag-NPs against SARS-CoV-2 virus, surface factors that influence viral persistence on fomites, the necessity of antiviral PPEs, and the potential application of amine-functionalized silver nanoparticles as a coating material for the development of trap and kill-efficient face masks and PPE kits.

Tunable Quantum Photoinitiators for Radical Photopolymerization.

This review describes the use of nanocrystal-based photocatalysts as quantum photoinitiators, including semiconductor nanocrystals (e.g., metal oxides, metal sulfides, quantum dots), carbon dots, graphene-based nanohybrids, plasmonic nanocomposites with organic photoinitiators, and tunable upconverting nanocomposites. The optoelectronic properties, cross-linking behavior, and mechanism of action of quantum photoinitiators are considered. The challenges and prospects associated with the use of quantum photoinitiators for processes such as radical polymerization, reversible deactivation radical polymerization, and photoinduced atom transfer radical polymerization are reviewed. Due to their unique capabilities, we forsee a growing role for quantum photoinitiators over the coming years.

Organotrialkoxysilane-Functionalized Prussian Blue Nanoparticles-Mediated Fluorescence Sensing of Arsenic(III).

Prussian blue nanoparticles (PBN) exhibit selective fluorescence quenching behavior with heavy metal ions; in addition, they possess characteristic oxidant properties both for liquid-liquid and liquid-solid interface catalysis. Here, we propose to study the detection and efficient removal of toxic arsenic(III) species by materializing these dual functions of PBN. A sophisticated PBN-sensitized fluorometric switching system for dosage-dependent detection of As3+ along with PBN-integrated SiO2 platforms as a column adsorbent for biphasic oxidation and elimination of As3+ have been developed. Colloidal PBN were obtained by a facile two-step process involving chemical reduction in the presence of 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane (EETMSi) and cyclohexanone as reducing agents, while heterogeneous systems were formulated via EETMSi, which triggered in situ growth of PBN inside the three-dimensional framework of silica gel and silica nanoparticles (SiO2). PBN-induced quenching of the emission signal was recorded with an As3+ concentration (0.05-1.6 ppm)-dependent fluorometric titration system, owing to the potential excitation window of PBN (at 480-500 nm), which ultimately restricts the radiative energy transfer. The detection limit for this arrangement is estimated around 0.025 ppm. Furthermore, the mesoporous and macroporous PBN-integrated SiO2 arrangements might act as stationary phase in chromatographic studies to significantly remove As3+. Besides physisorption, significant electron exchange between Fe3+/Fe2+ lattice points and As3+ ions enable complete conversion to less toxic As5+ ions with the repeated influx of mobile phase. PBN-integrated SiO2 matrices were successfully restored after segregating the target ions. This study indicates that PBN and PBN-integrated SiO2 platforms may enable straightforward and low-cost removal of arsenic from contaminated water.

Organotrialkoxysilane-Functionalized Noble Metal Monometallic, Bimetallic, and Trimetallic Nanoparticle Mediated Non-Enzymatic Sensing of Glucose by Resonance Rayleigh Scattering.

Organotrialkoxysilanes like 3-aminopropyltrimethoxysilane (3-APTMS)-treated noble metal cations were rapidly converted into their respective nanoparticles in the presence of 3-glycidoxypropylytrimethoxysilane (3-GPTMS). The micellar activity of 3-APTMS also allowed us to replace 3-GPTMS with other suitable organic reagents (e.g., formaldehyde); this approach has significant advantages for preparing bimetallic and trimetallic analogs of noble metal nanoparticles that display efficient activity in many practical applications. The formation of monometallic gold, silver, and palladium nanoparticles, bimetallic Ag-Pd, and Au-Pd nanoparticles at various ratios of noble metal cations, and trimetallic Ag-Au-Pd nanoparticles were studied; their biocatalytic activity in non-enzymatic sensing of glucose based on monitoring synchronous fluorescence spectroscopy (SFS) was assessed. Of these nanoparticles, Au-Pd made with an 80:20 Au:Pd ratio displayed excellent catalytic activity for glucose sensing. These nanoparticles could also be homogenized with Nafion to enhance the resonance Rayleigh scattering (RRS) signal. In this study, the structural characterization of noble metal nanoparticles as well as bi- and tri-metallic nanoparticles in addition to their use in non-enzymatic sensing of glucose are reported.

Synthetic incorporation of palladium-nickel bimetallic nanoparticles within mesoporous silica/silica nanoparticles as efficient and cheaper catalyst for both cationic and anionic dyes degradation.

Nickel-palladium bimetallic nanocrystallite supported mesoporous silica/silica nanoparticles (MSPs/MSNPs) made at a controlled ratio of Pd/Ni via organotrialkoxysilane mediated reduction of palladium cations are reported. The organotrialkoxysilane serve as a template for the stabilization and formation of bimetallic Pd-Ni nanocrystallite within MSPs/MSNPs that are characterized by TEM, EDX, HR-SEM, HR-MS, XRD, BET and Elemental mapping analysis, kinetic analysis for degradation of both cationic and anionic dyes, i.e., rhodamine B and congo red, respectively. The nanocrystallite inserted MSNPs of particle diameter 200 nm justify faster degradation with rate constant to the order of 6.9 x10-2s-1 as compared to that for MSPs of 50 µm to the order of 3.2 x10-2 s-1 for 15 ppm Rh B within 50 s as compared to that for mesoporous silica of 50 µm within 110 s under similar conditions with analogous observation for the degradation of congo red. Heterogeneous support is fully recyclable and shows 100% catalytic activity even after five subsequent applications. The degradation dynamics have further been evaluated based on fluorescent spectra and HR-MS analysis.

Nanostructured diamond for biomedical applications.

Nanostructured forms of diamond have been recently considered for use in a variety of medical devices due to their unusual biocompatibility, corrosion resistance, hardness, wear resistance, and electrical properties. This review considers several routes for the synthesis of nanostructured diamond, including chemical vapor deposition, hot filament chemical vapor deposition, microwave plasma-enhanced chemical vapor deposition, radio frequency plasma-enhanced chemical vapor deposition, and detonation synthesis. The properties of nanostructured diamond relevant to medical applications are described, including biocompatibility, surface modification, and cell attachment properties. The use of nanostructured diamond for bone cell interactions, stem cell interactions, imaging applications, gene therapy applications, and drug delivery applications is described. The results from recent studies indicate that medical devices containing nanostructured diamond can provide improved functionality over existing materials for the diagnosis and treatment of various medical conditions.

Microneedle-based transdermal electrochemical biosensors based on Prussian blue-gold nanohybrid modified screen-printed electrodes.

We report on the fabrication of a microneedle-based electrochemical biosensor for use in transdermal biosensing, which includes a screen-printed electrode containing a Prussian blue-gold nanohybrid as the working electrode. The Prussian blue gold nanohybrid is made from polyethylenime (PEI)- mediated simultaneous synthesis of Prussian blue (PBNP) and gold nanoparticles (AuNP), which forms a PBNP-AuNP nanohybrid with a remarkable change in the Prussian blue character. PEI-protected polycrystalline PBNPs can be synthesized in acidic media from the single precursor potassium ferricyanide [K3 Fe(CN)6 ] at 60°C. Since PEI also enables the controlled formation of gold nanoparticles (AuNPs) in the presence of formaldehyde, nanohybrids containing PBNPs and AuNPs may be prepared. Two different methods of PEI mediated synthesis of AuNP in the presence of PBNP were considered. In Method 1, AuNP and PBNP were made independently and mixed together in an appropriate ratio. In Method 2, PBNPs were made first, followed by PEI- and formaldehyde-mediated reduction of gold cations in the presence of PBNP. PBNP-AuNPs display a remarkable change in Prussian blue behavior such that the absorption maxima of PBNP-AuNPs made through Method 1 tend to increase at 670 nm as a function of gold concentration as compared with the control; the reverse was observed when PBNP-AuNPs were made through Method 2. As made PBNPs and PBNP-AuNPs made through Method 1 display excellent catalytic activity toward both reduction and oxidation of hydrogen peroxide based on peroxidase mimetic activity. In addition, the as-synthesized PBNPs displayed superparamagnetic behavior that can be manipulated in the presence of AuNPs. The results from peroxidase mimetic activity, chemiluminescence, cyclic voltammetry, and amperometry showed suitable analytical performance of the as-made PBNP-AuNP nanohybrid for biomedical applications.

Minimally Invasive Platforms in Biosensing.

The interaction of sensing components with body fluids is a basic requirement for clinical diagnostics; a variety of novel platforms have recently been developed for invasive and non-invasive sensing. In this manuscript, recent advancements related to minimally invasive platform for biosensing are reviewed. Many approaches have been utilized for generating minimally invasive platforms that require a small volume of body fluid; for example, the use of small-scale needles known as microneedles for minimally invasive detection has been demonstrated. The use of capillary action in microneedle-assisted biosensing may facilitate the detection of analytes in body fluids. This review considers recent innovations in the structure and performance of minimally invasive sensos.

Molecular weight of polyethylenimine-dependent transfusion and selective antimicrobial activity of functional silver nanoparticles.

Synthetic cationic polymer-mediated synthesis of silver nanoparticles and selective antimicrobial activity of the same were demonstrated. Polyethyleneimine (PEI)-coated silver nanoparticles showed antimicrobial activity against Acinetobacter baumannii as a function of the polymeric molecular weight (MW) of PEI. Silver nanoparticles were coated with PEI of three different MWs: Ag-NP-1 with PEI exhibiting a MW of 750,000, Ag-NP-2 with PEI exhibiting a MW of 1300, and Ag-NP-3 with PEI exhibiting a MW of 60,000. These nanoparticles showed a particle size distribution of 4-20 nm. The nanoparticles exhibited potent antimicrobial activity against A. baumannii, with the minimum inhibitory concentration of Ag-NP-1, Ag-NP-2, and Ag-NP-3 on the order of 5, 10, and 5 µg/mL, respectively, and minimum bactericidal concentration of Ag-NP-1, Ag-NP-2, and Ag-NP-3 on the order of 10, 20, and 10 µg/mL, respectively. Fluorescence imaging of Ag-NPs revealed selective transfusion of Ag-NPs across the cell membrane as a function of the polymeric MW; differential interaction of the cytoplasmic proteins during antimicrobial activity was observed.

Current Advancements in Transdermal Biosensing and Targeted Drug Delivery.

In this manuscript, recent advancements in the area of minimally-invasive transdermal biosensing and drug delivery are reviewed. The administration of therapeutic entities through the skin is complicated by the stratum corneum layer, which serves as a barrier to entry and retards bioavailability. A variety of strategies have been adopted for the enhancement of transdermal permeation for drug delivery and biosensing of various substances. Physical techniques such as iontophoresis, reverse iontophoresis, electroporation, and microneedles offer (a) electrical amplification for transdermal sensing of biomolecules and (b) transport of amphiphilic drug molecules to the targeted site in a minimally invasive manner. Iontophoretic delivery involves the application of low currents to the skin as well as the migration of polarized and neutral molecules across it. Transdermal biosensing via microneedles has emerged as a novel approach to replace hypodermic needles. In addition, microneedles have facilitated minimally invasive detection of analytes in body fluids. This review considers recent innovations in the structure and performance of transdermal systems.

Beat-to-beat estimation of stroke volume using impedance cardiography and artificial neural network.

Impedance cardiography is a low-cost noninvasive technique, based on monitoring of the thoracic impedance, for estimation of stroke volume (SV). Impedance cardiogram (ICG) is the negative of the first derivative of the impedance signal. A technique for beat-to-beat SV estimation using impedance cardiography and artificial neural network (ANN) is proposed. A three-layer feed-forward ANN with error back-propagation algorithm is optimized by examining the effects of number of neurons in the hidden layer, activation function, training algorithm, and set of input parameters. The input parameters are obtained by automatic detection of the ICG characteristic points, and the target values are obtained by beat-to-beat SV measurements from time-aligned Doppler echocardiogram. The technique is evaluated using an ICG-echocardiography database with recordings from subjects with normal health in the under-rest and post-exercise conditions and from subjects with cardiovascular disorders in the under-rest condition. The proposed technique performed much better than the earlier established equation-based estimations, and it resulted in correlation coefficient of 0.93 for recordings from subjects with cardiovascular disorders. It may be helpful in improving the acceptability of impedance cardiography in clinical practice. Graphical abstract ᅟ.

3-Aminopropyltrimethoxysilane mediated solvent induced synthesis of gold nanoparticles for biomedical applications.

The effect of acetone on 3-aminopropyltrimethoxysilane (3-APTMS) mediated synthesis of gold nanoparticles (AuNPs) in polar protic, polar aprotic and non polar solvents specifically water, acetone and chloroform has been studied. The findings revealed that acetone promotes the formation of siloxane polymer in chloroform and acetone solvents, but not in water, while AuNPs are formed in all cases. The bifunctional nature of 3-APTMS [NH2(CH2)3Si(OMe)3] controls the formation of siloxane polymer through hydrolysis and condensation of trimethoxysilyl group whereas the amine moieties are likely to form imine linkage, which are involved in the synthesis of gold nanoparticles. The siloxane polymer with imine linkage can be formed both in absence and the presence of gold precursor (i.e. HAuCl4). Accordingly, siloxane-gold nanoparticles can be made in different morphology, through control over the process, in three ways; (i) all precursors (Au3+, 3-APTMS and acetone) mixed simultaneously yielding [(siloxane-Ausim)], (ii) polymer made first followed by sequential reduction of Au3+ in homogenous suspension forming (Au-siloxanehomo)seq and (iii) polymer made into thin film followed by sequential reduction of Au3+ in the heterogeneous system yielding (Au-siloxanehetero)seq. The AuNPs produced with the use of water as solvent is different from the three described above as discrete spherical AuNPs are formed as [(AuNPs)water] and in this case siloxane polymer is not formed. The results based on AFM and SEM characterizations revealed porous morphology of NPs fabricated in chloroform/acetone, due to the formation of siloxane polymer, and non-porous morphology for the same in water. The "(Au-siloxanehetero)seq" efficiently promote the reduction of p-nitrophenol with good operational stability, justifying its interest for heterogeneous catalysis. On the other hand, (siloxane-Ausim) and (Au-siloxanehomo)seq can be also deposited onto glassy carbon surfaces to yield polymer modified electrodes for subsequent electroanalytical applications. The cyclic voltammetry response of such modified electrodes to a redox probe (i.e., Fe(CN)63-/4-) was characteristic of diffusion controlled and thin-layer electrochemical behaviour respectively as a function of non-porous and porous nature of the polymer. The as made nanomaterial shows excellent biocatalyst for dopamine sensing based on peroxidase mimetic activity. The typical result on dopamine sensing is reported.

Polyethylenimine-mediated synthetic insertion of gold nanoparticles into mesoporous silica nanoparticles for drug loading and biocatalysis.

Mesoporous silica nanoparticles (MSNPs) have been used as an efficient and safe carrier for drug delivery and biocatalysis. The surface modification of MSNPs using suitable reagents may provide a robust framework in which two or more components can be incorporated to give multifunctional capabilities (e.g., synthesis of noble metal nanoparticles within mesoporous architecture along with loading of a bioactive molecule). In this study, the authors reported on a new synthetic route for the synthesis of gold nanoparticles (AuNPs) within (1) unmodified MSNPs and (2) 3-trihydroxysilylpropyl methylphosphonate-modified MSNPs. A cationic polymer, polyethylenimine (PEI), and formaldehyde were used to mediate synthetic incorporation of AuNPs within MSNPs. The AuNPs incorporated within the mesoporous matrix were characterized by transmission electron microscopy, energy dispersive x-ray analysis, and high-resolution scanning electron microscopy. PEI in the presence of formaldehyde enabled synthetic incorporation of AuNPs in both unmodified and modified MSNPs. The use of unmodified MSNPs was associated with an increase in the polycrystalline structure of the AuNPs within the MSNPs. The AuNPs within modified MSNPs showed better catalytic activity than those within unmodified MSNPs. MSNPs with an average size of 200 nm and with a pore size of 4-6 nm were used for synthetic insertion of AuNPs. It was found that the PEI coating enabled AuNPs synthesis within the mesopores in the presence of formaldehyde or tetrahydrofuran hydroperoxide at a temperature between 10 and 25 °C or at 60 °C in the absence of organic reducing agents. The as-made AuNP-inserted MSNPs exhibited enhanced catalytic activity. For example, these materials enabled rapid catalytic oxidation of the o-dianisidine substrate to produce a colored solution in proportion to the amount of H2O2 generated as a function of glucose oxidase-catalyzed oxidation of glucose; a linear concentration range from 80 to 800 µM and a detection limit as low as 80 µM were observed. The mesoscale pores of the as developed AuNP-inserted MSNPs were also used to entrap the hydrophobic drug paclitaxel. The results of this study indicate the potential use of the AuNP-inserted MSNPs in biocatalysis and drug delivery.