Fluorescent silica nanoparticles as nano-chemosensors for the sequential detection of Pb2+ ions and bacterial-spore biomarker dipicolinic acid (DPA) in aqueous solution.

Herein, we report fluorescein-labelled silica nanoparticles (FSNP) which serve as fluorescent nano-chemosensors for sequential detection of Pb2+ (which is a toxic heavy metal) and dipicolinic acid (DPA) (which is a distinctive indicator biomarker of bacterial spores) with high sensitivity and selectivity. The fluorescence of FSNP is quenched because of the complex formation between Pb2+ ions and surface amide groups, however, the fluorescence is recovered in contact with DPA, resulting from the association of DPA with surface bound Pb2+ ions. FSNP-Pb2+ complexes show high sensitivity towards DPA with a low detection limit of 850 nM which is approximately seventy times lower than the infectious dosage of bacterial spores (60 µM). Lateral flow test platform was further developed to show the applicability and practicability of our system.

Reactive Extraction of Betaine from Sugarbeet Processing Byproducts.

Betaine from natural sources is still preferred over its synthetic analogue in secondary industries. It is currently obtained by expensive separation means, which is one of the main reasons for its high cost. In this study, reactive extraction of betaine from sugarbeet industry byproducts, that is, molasses and vinasse, was investigated. Dinonylnaphthalenedisulfonic acid (DNNDSA) was used as the extraction agent, and the initial concentration of betaine in the aqueous solutions of byproducts was adjusted to 0.1 M. Although maximum efficiencies were obtained at unadjusted pH values (pH 6, 5, and 6 for aqueous betaine, molasses, and vinasse solutions, respectively), the effect of aqueous pH on betaine extraction was negligible in the range of 2-12. The possible reaction mechanisms between betaine and DNNDSA under acidic, neutral, and basic conditions were discussed. Increasing the extractant concentration significantly increased (especially in the range of 0.1-0.4 M) the yields, and temperature positively (but slightly) affected betaine extraction. The highest extraction efficiencies (∼71.5, 71, and 67.5% in a single step for aqueous betaine, vinasse, and molasses solutions, respectively) were obtained with toluene as an organic phase solvent, and it was followed by dimethyl phthalate, 1-octanol, or methyl isobutyl ketone, indicating that the efficiency increased with decreasing polarity. Recoveries from pure betaine solutions were higher (especially at higher pH values and [DNNDSA] < 0.5 M) than those from vinasse and molasses solutions, indicating the adverse influence of byproduct constituents; however, the lower yields were not due to sucrose. Stripping was affected by the type of organic phase solvent, and a significant amount (66-91% in single step) of betaine in the organic phase was transferred to the second aqueous phase using NaOH as the stripping agent. Reactive extraction has a great potential for use in betaine recovery due to its high efficiency, simplicity, low energy demand, and cost.

A Dicationic BODIPY-Based Fluorescent Bactericide to Combat Infectious Diseases and to Eradicate Bacterial Biofilms.

Increased bacterial resistance against extensively used common disinfectants has begun to emerge. The discovery of disinfectants substituting the current commercially available ones is strongly needed. For this purpose, a dicationic BODIPY-based fluorescent amphiphile has been synthesized by specific molecular design. This quaternized BODIPY behaves as a broad-spectrum disinfectant against both Gram-positive and Gram-negative bacteria strains. It exhibits potent antimicrobial activity against tested microorganisms when compared with structurally similar disinfectant benzalkonium chloride (BAC). Moreover, it shows antibiofilm activity against Staphylococcus epidermidis with a minimum biofilm eradication concentration as low as 16 µg/mL. The interaction of this compound with the bacterial cell and genomic DNA was further evaluated by fluorescence spectroscopy and microscopy to follow cell internationalization and to clarify the mechanism of antibacterial action.

Development of electrochemical aptasensors detecting phosphate ions on TMB substrate with epoxy-based mesoporous silica nanoparticles.

This study, it is aimed to develop an electrochemical aptasensor that can detect phosphate ions using 3.3'5.5' tetramethylbenzidine (TMB). It is based on the principle of converting the binding affinity of the target molecule phosphate ion (PO43-) into an electrochemical signal with specific aptamer sequences for the aptasensor to be developed. The aptamer structure served as a gate for the TMB to be released and was used to trap the TMB molecule in mesoporous silica nanoparticles (MSNPs). The samples for this study were characterized by transmission electron spectroscopy (TEM), Brunner-Emmet-Teller, dynamic light scattering&electrophoretic light scattering, and induction coupled plasma atomic emission spectroscopy. According to TEM analysis, MSNPs have a morphologically hexagonal structure and an average size of 208 nm. In this study, palladium-carbon nanoparticles (Pd/C NPs) with catalytic reaction were used as an alternative to the biologically used horseradish peroxidase (HRP) enzyme for the release of TMB in the presence of phosphate ions. The limit of detection (LOD) was calculated as 0.983 µM, the limit of determination (LOQ) was calculated as 3.276 µM, and the dynamic linear phosphate range was found to be 50-1000 µM. The most important advantage of this bio-based aptasensor assembly is that it does not contain molecules such as a protein that cannot be stored for a long time at room temperature, so its shelf life is very long compared to similar systems developed with antibodies. The proposed sensor shows good recovery in phosphate ion detection and is considered to have great potential among electrochemical sensors.

High-efficiency application of CTS-Co NPs mimicking peroxidase enzyme on TMB(ox).

In this study, analytical studies of Chitosan-Cobalt(II) (CTS-Co(II)) nanoparticles (CTS - Co NPs) by mimicking horseradish peroxidase (HRP) were evaluated. In the applications, it was observed that CTS-Co NPs 3,3' 5,5' tetramethylbenzidine (TMB) oxidized in the presence of hydrogen peroxide (H2O2). The required CTS-Co NPs were synthesized at 50 °C in 30 min and characterized using Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and X-ray photon spectroscopy (XPS) was done. CTS-Co NPs were studied to develop a selective TMB biosensor on TMB(ox) substrate. The synthesized CTS-Co NPs formed a catalytic reaction with 30% 0.2 mM H2O2 on 0.2 M TMB substrate. After the catalytic reaction, sensitive signals were obtained from the desired biosensor. Electrochemical measurements were taken as low limit of 10 mg and a high limit of 20 mg for the determination of CTS-Co NPs to TMB(ox). In the microplate study; The sensors were applied on 1.5 µg and 3 µg CTS-Co NPs TMB(ox) substrate, respectively. CTS- Co NPs; for TMB(ox) determination, optical density (OD) measurement was taken as a low limit of 1.5 µg and a high limit of 3 µg. Electrochemical applications of particles and microplate reader results were compared with horseradish peroxidase (HRP) enzyme for sensor properties. According to the data obtained, it was observed that it behaved similarly to the CTS-Co NPs peroxidase enzyme. This work presents innovations for nanoparticle extraction and sensor study from chitosan and other naturally sourced polymers.

A novel ratiometric and colorimetric probe for rapid and ultrasensitive detection of nitrite in water based on an Acenaphtho[1,2-d] imidazole derivative.

The concentration of nitrite (NO2-) ions above allowable limits in water resources and food stuffs is considered hazardous and has been proven to be of great threat to the environment and public health. In this work, an acenaphtho [1,2-d] imidazole derivative (1) as a ratiometric colorimetric probe is developed. UV-Vis experiments demonstrate that the probe 1 shows excellent selectivity toward NO2- in the presence of other potential interfering species, a rapid response (20 s) and a low detection limit (100 nM) by a distinct visual color change with a bathochromic shift of 120 nm from colorless to intense yellow. Besides, this probe is further used for the quantification of nitrite ions in environmental water resources such as tap water, underground water, and surface water samples. The high recoveries (96-99% with relative standard deviations (RSD) of <2.0%) make the probe 1 a promising candidate for practical applications in daily life in the detection of nitrite ions.

Catalytic evaluation of biocompatible chitosan-stabilized gold nanoparticles on oxidation of morin.

Herein, we present a study on the catalytic evaluation of biocompatible chitosan-stabilized gold nanoparticles (CH-AuNPs) on the oxidation of morin as a model reaction. Biocompatible CH-AuNPs have been characterized through several analytical methods such as TEM, UV-vis, DLS and zeta potential analyses. CH-AuNPs have a small size (10 ± 0.4 nm) with a narrow size distribution and high positive surface charge (+40.1 mV). CH-AuNPs has been demonstrated to be highly active nanocatalysts for the oxidation of morin with the assistance of H2O2 as an oxidant compared with control experiments. The oxidation reaction follows a pseudo-first-order reaction. The kinetic studies show that apparent rate constant (kapp) is positively correlated with the concentrations of CH-AuNPs and H2O2, while it is negatively correlated with morin concentration. Furthermore, the reusability tests have been performed and the results demonstrate the long-term stability and reusability of CH-AuNPs without any loss of catalytic activity. Cytotoxicity studies exhibit that CH-AuNPs have low toxicity and they are biocompatible with HeLa and MCF-7 cells.

A highly substituted and fluorescent aromatic-fused imidazole derivative that shows enhanced antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA).

A novel highly substituted and fluorescent aromatic-fused imidazole derivative has been synthesized by rational design. This novel fluorescent material acts as an alternative antibacterial agent against Gram positive bacteria strains. It shows superior antibacterial activity (with MIC value of 8 µg/mL) against methicillin-resistant Staphylococcus aureus (MRSA) when compared with standard antibiotic drugs Ampicillin (with MIC value of 128 µg/mL) and Kanamycin (with MIC value of >512 µg/mL). The interaction of this novel compound with the bacterial cell and genomic DNA has also been studied to elucidate antibacterial mode of action. Fluorescence spectroscopy and microscopy studies have proved the intracellular uptake of this special compound. Likewise, UV-vis and fluorescence spectroscopy studies have revealed a significant decrease in the absorption and emission bands of the compound upon its interaction with plasmid and genomic DNA, which is likely due to its DNA intercalation property. Furthermore, these findings have been supported by gel electrophoresis of genomic DNA of S. aureus cells treated with the compound. The results indicate that this novel compound exerts its antibacterial activity by causing DNA damage, suggesting the potential utility of fluorescent probes for real-time diagnosis and treatment of bacterial infections.

Luminescent detection of Ochratoxin A using terbium chelated mesoporous silica nanoparticles.

This work represents the time-resolved fluorescence detection of Ochratoxin A (OTA), a highly toxic and commonly found toxin in food stuffs, by a terbium (Tb3+) chelated nanoparticle sensor with high sensitivity and remarkable selectivity. The coordination of OTA to Tb3+ center on nanoparticle surface resulted in the significant enhancement of the fluorescence signal in nanomolar concentrations with a detection limit of 20 ppb. In contrast, no enhancements were observed in the presence of other common mycotoxins such as Aflatoxin B1, Zearalenone, Citrinin and Patulin. The results indicate that the Tb3+ chelated nanoparticle sensor has great potential for applications in food analysis and safety.

Effect of feed supplementation with biosynthesized silver nanoparticles using leaf extract of Morus indica L. V1 on Bombyx mori L. (Lepidoptera: Bombycidae).

Herein, we report the synthesis of silver nanoparticles (AgNPs) by a green route using the aqueous leaf extract of Morus indica L. V1. The synthesized AgNPs exhibited maximum UV-Vis absorbance at 460 nm due to surface plasmon resonance. The average diameter (~54 nm) of AgNPs was measured from HR-TEM analysis. EDX spectra also supported the formation of AgNPs, and negative zeta potential value (-14 mV) suggested its stability. Moreover, a shift in the carbonyl stretching (from 1639 cm-1 to 1630 cm-1) was noted in the FT-IR spectra of leaf extract after AgNPs synthesis which confirm the role of natural products present in leaves for the conversion of silver ions to AgNPs. The four bright circular rings (111), (200), (220) and (311) observed in the selected area electron diffraction pattern are the characteristic reflections of face centered cubic crystalline silver. LC-MS/MS study revealed the presence of phytochemicals in the leaf extract which is responsible for the reduction of silver ions. MTT assay was performed to investigate the cytotoxicity of AgNPs against two human cell lines, namely HepG2 and WRL-68. The antibacterial study revealed that MIC value of the synthesized AgNPs was 80 µg/ml against Escherichia coli K12 and Staphylococcus aureus (MTCC 96). Finally, the synthesized AgNPs at 10 µg/ml dosages showed beneficial effects on the survivability, body weights of the Bombyx mori L. larvae, pupae, cocoons and shells weights via enhancing the feed efficacy.

A Monostyryl Boradiazaindacene (BODIPY)-based lanthanide-free colorimetric and fluorogenic probe for sequential sensing of copper (II) ions and dipicolinic acid as a biomarker of bacterial endospores.

A new catechol-substituted monostyryl boradiazaindacene (BODIPY)-based lanthanide-free colorimetric and fluorogenic probe was developed for the sequential detection of Cu2+ ions and dipicolinic acid (DPA), a distinctive biomarker of bacterial endospores, with high sensitivity and selectivity. In the presence of Cu2+ ions, the blue solution of the probe changes to cyan and the fluorescence is quenched, however, the cyan color changes to blue immediately and the fluorescence is restored on contact with DPA, resulting from competitive binding of DPA that interact with Cu2+ ions. A practical application by using Geobacillus stearothermophilus spores was further studied and as low as 1.0 x 105 spores were detected.

Green synthesis of silver nanoparticles: biomolecule-nanoparticle organizations targeting antimicrobial activity.

Since discovery of the first antibiotic drug, penicillin, in 1928, a variety of antibiotic and antimicrobial agents have been developed and used for both human therapy and industrial applications. However, excess and uncontrolled use of antibiotic agents has caused a significant growth in the number of drug resistant pathogens. Novel therapeutic approaches replacing the inefficient antibiotics are in high demand to overcome increasing microbial multidrug resistance. In the recent years, ongoing research has focused on development of nano-scale objects as efficient antimicrobial therapies. Among the various nanoparticles, silver nanoparticles have gained much attention due to their unique antimicrobial properties. However, concerns about the synthesis of these materials such as use of precursor chemicals and toxic solvents, and generation of toxic byproducts have led to a new alternative approach, green synthesis. This eco-friendly technique incorporates use of biological agents, plants or microbial agents as reducing and capping agents. Silver nanoparticles synthesized by green chemistry offer a novel and potential alternative to chemically synthesized nanoparticles. In this review, we discuss the recent advances in green synthesis of silver nanoparticles, their application as antimicrobial agents and mechanism of antimicrobial mode of action.

Enhanced antitumor activity of carbendazim on HeLa cervical cancer cells by aptamer mediated controlled release.

Carbendazim, is a broad-spectrum fungicide and also a promising experimental antitumor drug as reproduction and developmental toxicant, which is currently under phase II preclinical trials. In this study, an approach based on controlled and targeted release with aptamers and mesoporous silica nanoparticles was investigated to improve the antitumor activity of carbendazim. To this end, we synthesized aptamer conjugated silica nanoparticles for testing cytotoxicity properties in vitro with human cervical adenocarcinoma (HeLa) cultured cells. Nucleolin (AS1411) binding aptamers were used to entrap carbendazim molecules inside nanopores of MCM-41 type silica nanoparticles to obtain a stimuli-dependent release system. The effect of carbendazim loaded aptamer silica complex was tested and compared to free carbendazim treatment on HeLa cells, demonstrating 3.3 fold increase of toxicity on targeted cells with our delivery system. In addition, cytotoxicity of the complex was determined to be mostly due to increased apoptosis and to a less extend necrosis related pathways.

Eriochrome Black T-Eu3+ Complex as a Ratiometric Colorimetric and Fluorescent Probe for the Detection of Dipicolinic Acid, a Biomarker of Bacterial Spores.

A novel ratiometric colorimetric and fluorescent dual probe based on Eriochrome Black T (EBT)-Eu3+ complex was designed to detect dipicolinic acid (DPA), a major constituent of bacterial spores, with high sensitivity and selectivity. UV-vis titration experiments demonstrated that EBT and Eu3+ ions formed a 1:1 coordination pair in water. In the presence of Eu3+ ions, the blue solution of EBT changed to magenta, however, upon the addition of DPA, the magenta color changed to blue immediately and characteristic fluorescence emission from DPA-Eu3+ complex was observed. In addition, the sensitivity of the system was further evaluated on Geobacillus stearothermophilus spores and as low as 2.5 × 105 spores were detected.

Ratiometric fluorescence detection of an anthrax biomarker with Eu3+-chelated chitosan biopolymers.

A novel chitosan-based ratiometric fluorescent probe incorporating an EDTA-Eu3+ complex as the sensing unit and fluorescein dye as the internal standard was designed to detect dipicolinic acid (DPA) as an anthrax biomarker with high sensitivity and selectivity. The fluorescence intensity of fluorescein dye attached to the chitosan backbone remains constant as an internal reference, while the Eu3+ emission increased linearly upon the consecutive addition of DPA. The selectivity studies were performed by adding different competitive aromatic ligands to the sensing environment and no signifacant fluorescence response was observed. The results demonstrated the superior selectivity of the system to DPA. Overall, this novel chitosan-based ratiometric fluorescent probe enables ratiometric and sensitive DPA detection over nanomolar concentrations (as low as 10nM) and displays straightforward selectivity over other competitive aromatic ligands.

Fluorescent detection of dipicolinic acid as a biomarker of bacterial spores using lanthanide-chelated gold nanoparticles.

Gold nanoparticles (GNPs) functionalized with ethylenediamine-lanthanide complexes (Eu-GNPs and Tb-GNPs) were used for the selective fluorescent detection of dipicolinic acid (DPA), a unique biomarker of bacterial spores, in water. Particles were characterized by transmission electron microscopy and zeta potential measurements. The coordination of DPA to the lanthanides resulted in the enhancement of the fluorescence. A selective response to DPA was observed over the nonselective binding of aromatic ligands. The ligand displacement strategy were also employed for the ratiometric fluorescent detection of DPA. 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedion (TFNB) was chosen as an antenna to synthesize ternary complexes. The addition of DPA on EuGNP:TFNB ternary complex quenched the initial emission of the complex at 615nm and increased the TFNB emission at 450nm when excited at 350nm. The results demonstrated that the ratiometric fluorescent detection of DPA was achieved by ligand displacement strategy.

Layer-by-layer hyaluronic acid/chitosan polyelectrolyte coated mesoporous silica nanoparticles as pH-responsive nanocontainers for optical bleaching of cellulose fabrics.

Polyelectrolyte multilayer (PEM) films composed of two natural polysaccharides (hyaluronic acid and chitosan) were deposited through layer-by-layer (LbL) assembly on top of biocompatible mesoporous silica nanoparticles (MSNPs). Polyelectrolyte multilayer coated mesoporous silica nanoparticles (PEM-MSNPs) were characterized by using attenuated total reflection-fourier transform infrared spectroscopy (ATR-FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherms, UV-vis and fluorescence spectrophotometer. A commercially available and industrially used optical brightener, 4,4'-distyrylbiphenyl sulfonate sodium salt (CBSX) was loaded into nanocontainers (CBSX@PEM-MSNPs) to evaluate their use for the pH-sensitive release. The controlled release of CBSX from nanocontainers in response to pH is monitored by using UV-vis and fluorescence spectrophotometer in water and the almost 100% of encapsulated CBSX is released within 2h at pH 7. The increase in both whiteness and total color change at pH 7 on a cellulose fabric demonstrates the great potential of nanocontainers as pH-sensitive whitening agents for optical bleaching of cellulose fabrics.

Esterase- and pH-responsive poly(ß-amino ester)-capped mesoporous silica nanoparticles for drug delivery.

Gating of mesoporous silica nanoparticles (MSNs) with the stimuli-responsive poly(ß-amino ester) has been achieved. This hybrid nanocarrier releases doxorubicin (DOX) under acidic conditions or in the presence of porcine liver esterase. The DOX loaded poly(ß-amino ester)-capped MSNs reduce cell viability when tested on MDA-MB-231 human breast cancer cells.

Sugar and pH dual-responsive mesoporous silica nanocontainers based on competitive binding mechanisms.

A sugar and pH dual-responsive controlled release system, which is highly specific towards molecular stimuli, has been developed based on the binding between catechol and boronic acid on a platform of mesoporous silica nanoparticles (MSNs). By grafting phenylboronic acid stalks onto the silica surface, catechol-containing ß-cyclodextrins can be attached to the orifices of the MSNs' nanopores through formation of boronate esters which block access to the nanopores. These esters are stable enough to prevent cargo molecules from escaping. The boronate esters disassociate in the presence of sugars, enabling the molecule-specific controlled-release feature of this hybrid system. The rate of release has been found to be tunable by varying both the structures and the concentrations of sugars, as a result of the competitive binding nature associated with the mechanism of its operation. Acidification also induces the release of cargo molecules. Further investigations show that the presence of both a low pH and sugar molecules provides cooperative effects which together control the rate of release.

New methods for improved characterization of silica nanoparticle-based drug delivery systems.

The incorporation of silica nanoparticles into drug delivery vehicles, and other nanotech platforms, has experienced rapid and significant growth over the past decade. However, as these nanoparticle-based systems become more and more complex, the methods used to analyze these systems have evolved at a comparatively much slower pace, resulting in the need for researchers to expand their toolbox and devise new strategies to characterize these materials. This article describes how X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were recently employed in the analysis of two separate drug delivery systems which contain organic compounds covalently attached to the surfaces of silica nanoparticles. These techniques provided a deluge of qualitative and quantitative information about these drug delivery systems, and have several clear advantages over more common characterization procedures such as Fourier transform infrared spectroscopy (FT-IR) and solid state nuclear magnetic resonance (SSNMR). Thus, XPS and ToF-SIMS should be an integral component of the standard characterization protocol for any nanoparticle-based assemblies-particularly silica-based drug delivery systems-as this field of research continues to develop.