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Biomimetic composite materials consisting of vanadium pentoxide (V2O5) and a liquid crystal (LC) "gluing" polymer were manufactured exhibiting six structural levels of hierarchy, formed through LC phases. The organic matrix was a polyoxazoline with pendant cholesteryl and carboxyl units, forming a lyotropic phase with the same structural orientation extending up to hundreds of micrometers upon shearing, and binding to V2O5 via hydrogen bridges. Composites consisting of V2O5-LC polymer hybrid fibers with a pronounced layered structuring were obtained. The V2O5-LC polymer hybrid fibers consist of aligned V2O5 ribbons, composed of self-assembled V2O5 sheets, encasing a chiral nematic polymer matrix. The structures of the V2O5-LC polymer composites strongly depend on the preparation method, i.e., the phase-transfer method from aqueous to organic medium, in which the polymer forms LC phases. Notably, highly defined micro- and nanostructures were obtained when initiating the synthesis using V2O5 tactoids with preoriented nanoparticle building units, even when using isotropic V2O5 dispersions. Shear-induced hierarchical structuring of the composites was observed, as characterized from the millimeter and micrometer down to the nanometer length scales using complementary optical and electron microscopy, SAXS, μCT, and mechanical nanoindentation.

In this study, polymer-grafted magnetic nanoparticles containing chromium(iii) ions incorporated onto Fe3O4/mercaptopropanoic acid-poly(2-hydroxyethyl acrylate) (Fe3O4/MPA-PHEA-Cr) was prepared via a simple and in situ method. The obtained magnetic nanocomposite exhibited a high catalytic activity and excellent selectivity in the aerobic oxidation of alcohols under solvent-free conditions. The magnetic catalyst could also be separated by an external magnet and reused seven times without any significant loss of activity/selectivity.

A novel ultrasensitive photoelectrochemical immunosensor was fabricated based on 3-mercaptopropionic acid stabilized CdS/reduced graphene oxide (MPA-CdS/RGO) nanocomposites for indole-3-acetic acid (IAA) detection. The MPA-CdS/RGO nanocomposites were synthesized by in situ solvothermal growth of triangulated pyramidal CdS nanoparticles on the RGO sheet. 3-Mercaptopropionic acid (MPA) was employed as the modifier and bridge to immobilize the antibody. The nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy and UV/vis spectra. The results showed that the MPA-CdS/RGO nanocomposites revealed enhanced photocurrent response due to excellent electron transport properties of RGO and the improved assembly of CdS nanoparticles onto RGO sheet with the introduction of MPA. Based on the dependence of the photocurrent decline on the concentration of IAA, the proposed photoelectrochemical immunosensor for IAA depicted a linear range from 0.1 to 1000 ng/mL with a lower detection limit (0.05 ng/mL). The high sensitivity, reproducibility and specificity of the method permitted the method suitable to be used in real samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Two aroma compounds of volatile thiols, 2-furanmethanethiol (2FM) and ethyl 2-mercaptopropionate (ET2MP), were formed in five types of Japanese soy sauce during fermentation by yeast. The concentrations of 2FM and ET2MP in the soy sauce samples increased during alcoholic fermentation. The concentrations of 2FM and ET2MP were higher in the soy sauce fermented by Zygosaccharomyces rouxii than in that fermented by Candida versatilis. The enantiomers of ET2MP were separated by gas chromatography in a capillary column. The average enantiomeric ratio of ET2MP in the soy sauce was approximately 1:1. 2FM was formed by yeast in a medium prepared from cysteine and furfural, and cysteine is considered the key precursor of 2FM by yeast in soy sauce.

In this paper, a novel near-infrared fluorescence probe for the determination of 2,4,6-trinitrophenol (TNP) was developed based on bovine serum albumin (BSA) coated CuInS2 quantum dot (QD). Water-soluble CuInS2 QDs were directly synthesized in aqueous solution with mercaptopropionic acid (MPA) as stablizers, and it was coated by BSA via an amide link interacting with carboxyl of the MPA-capped CuInS2 QDs. The obtained BSA coated CuInS2 QDs (BSA-CuInS2 QDs) can bind TNP in water via the acid-base pairing interaction between electron-rich amino groups of BSA and electron-deficient nitroaromatic rings, and leading the fluorescence quenching of BSA-CuInS2 QDs. The quenched fluorescence intensity of BSA-CuInS2 QDs was proportional to the concentration of TNP in the concentration ranges from 50 nmol/L to 3.0 μmol/L. The detection limit (LOD) for TNP was 28 nmol/L. The developed fluorescence probe showed a excellent resistant to interference of metal ions such as K(+), Na(+), Zn(2+), Cu(2+), Hg(2+), and Pb(2+). The developed biosensor was applied to the determination of TNP in spiked water samples with satisfactory results., (© 2013 Elsevier B.V. All rights reserved.)

A liquid-to-solid gelling polymer system, such as the poly(ethylene glycol) diacrylate-pentaerythritol tetrakis (3-mercaptopropionate) (PEGDA-QT) system, can fill cerebral aneurysms more completely than current embolization materials, reducing the likelihood of aneurysm recurrence. PEGDA-QT gels were formulated using PEGDA of different molecular weights (PEGDA575 and PEGDA700), and their characteristics were examined in vitro. Experiments examined gel time, mass change, crosslink integrity, cytotoxicity, and protein release capabilities. In general, PEGDA575-QT gels were more hydrophobic, requiring an initiating solution with a higher pH (pH 9.5) to achieve a gel time comparable to PEGDA700-QT gels, which used an initiating solution at pH 9.19. The mass change and crosslink integrity of gels were analyzed over time after gels were submerged in 150 mM phosphate buffered saline. After 380 days, PEGDA575-QT gels achieved a maximum mass increase of 72% due to water uptake, while PEGDA700-QT gels doubled their initial mass (100% increase) by 165 days. Compression tests showed that PEGDA700-QT gels hydrolyzed more quickly than PEGDA575-QT gels. Cytotoxicity assays showed that in general, PEGDA575-QT negatively affected cell growth, while PEGDA700-QT gels promoted cell viability. Sustained, controlled release of lysozyme, a 14.3 kDa protein, was achieved over an 8-week period when loaded into PEGDA700-QT gels, but PEGDA575-QT gels did not show sustained release. These studies show that although they are similar in composition, these PEGDA-QT gel formulations behave considerably differently. Although PEGDA700-QT gels swell more and degrade faster than PEGDA575-QT gels, their cytocompatibility and protein release characteristics may prove to be more beneficial for in vivo aneurysm treatment., (Copyright © 2013 Wiley Periodicals, Inc.)

Describing the organization of substrates and substrate analogues in the active site of cysteine dioxygenase identifies potential intermediates in this critical yet poorly understood reaction, the oxidation of cysteine to cysteine sulfinic acid. The fortuitous formation of persulfides under crystallization conditions has allowed their binding in the active site of cysteine dioxygenase to be studied. The crystal structures of cysteine persulfide and 3-mercaptopropionic acid persulfide bound to iron(II) in the active site show that binding of the persulfide occurs via the distal sulfide and, in the case of the cysteine persulfide, the amine also binds. Persulfide was detected by mass spectrometry in both the crystal and the drop, suggesting its origin is chemical rather than enzymatic. A mechanism involving the formation of the relevant disulfide from sulfide produced by hydrolysis of dithionite is proposed. In comparison, persulfenate {observed bound to cysteine dioxygenase [Simmons, C. R., et al. (2008) Biochemistry 47, 11390]} is shown through mass spectrometry to occur only in the crystal and not in the surrounding drop, suggesting that in the crystalline state the persulfenate does not lie on the reaction pathway. Stabilization of both the persulfenate and the persulfides does, however, suggest the position in which dioxygen binds during catalysis.

Herein we present an unusual phosphine-free method to fabricate water soluble CdSeS nanocrystals in cubic structure. In this method, glycerin was used as a stabilizing agent replacing tri-n-octylphosphine oxide (TOPO). Water solution of Na2SeO3 in polyethylene glycol was utilized as Se source. 3-Mercaptopropionic acid (MPA) provides S source. The phosphine-free Se and S sources were found to be highly reactive and suitable for the synthesis of CdSeS nanocrystals. XRD and HRTEM images confirm the formation of CdSeS nanocrystals in zinc blende structure. The absorption peaks on UV-vis spectra of as-prepared CdSeS nanocrystals are tunable from 330 nm to 440 nm, which blue shifts to shorter wavelength side in comparison with that of pure CdSe nanocrystals. The cubic CdSeS nanocrystals demonstrate narrow PL emissions spectra between 464 and 615 nm. Transmission electron microscopy images show the uniformity for the size distribution of the ternary QDs. Series water soluble CdSe(1-x)S(x) (x = 0:1) nanocrystals have also been synthesized using Na2SeO3 and Na2S solution as the Se-S co-sources. Tunable band gap energies of CdSe(1-x)S(x) (x = 0:1) nanocrystals upon chemical composition x have been achieved, the gap ranges from 290 nm to 558 nm.

In this study, gold nanorods (GNRs) and graphene oxide (GO) were used to enhance the sensitivity of wavelength modulation surface plasmon resonance (SPR) biosensor to detect bovine IgG. GNRs were prepared by a method of seed-mediated growth and immobilized on the Au film through 1,6-hexanedithiol by covalent attachment. GO was prepared by a modified Hummers and Offeman's method and can be assembled on the sensor surface through electrostatic interaction with GNRs. Meanwhile, GO was used as a support to immobilize antibody directly. The biosensor based on GNRs/GO sensing membrane exhibits a satisfactory response for bovine IgG in the concentration range of 0.075-40.00 µg mL(-1). For comparison, the biosensor based on 3-mercaptopropinic acid (MPA) and the biosensor based on GNRs/MPA sensing membrane were also studied for the detection of bovine IgG. The biosensor based on MPA shows a response for bovine IgG in the concentration range of 2.50-40.00 µg mL(-1). The biosensor based on GNRs/MPA sensing membrane shows a response for bovine IgG in the concentration range of 0.30-40.00 µg mL(-1). As a result, the biosensor based on GNRs/GO sensing membrane was found to be the most sensitive of the three types of biosensors., (© 2013 Elsevier B.V. All rights reserved.)

Fluorescent quantum dots (QDs) have been widely applied in biological and biomedical areas, but relatively little is known about the interaction of QDs with some natural enzymes. Herein, the interactions between 3-mercaptopropionic acid-capped CdTe QDs (MPA-QDs) and papain were systematically investigated by UV-Vis absorption spectra, fluorescence spectra and circular dichroism (CD) spectra under the physiological conditions. The fluorescence spectra results indicated that MPA-QDs quenched the fluorescence intensity of papain. The modified Stern-Volmer quenching constant K a at different temperatures and the corresponding thermodynamic parameters ΔH, ΔG and ΔS were also calculated. The binding of MPA-QDs and papain is a result of the formation of QDs-papain complex and the electrostatic interactions play a major role in stabilizing the complex. The CD technique was further used to analyze the conformational changes of papain induced by MPA-QDs and the results indicated that the biological activity of papain was affected by MPA-QDs dramatically.

A novel quartz crystal microbalance (QCM) sensor for rapid, highly selective and sensitive detection of copper ions was developed. As a signal amplifier, gold nanoparticles (Au NPs) were self-assembled onto the surface of the sensor. A simple dip-and-dry method enabled the whole detection procedure to be accomplished within 20 min. High selectivity of the sensor towards copper ions is demonstrated by both individual and coexisting assays with interference ions. This gold nanoparticle mediated amplification allowed a detection limit down to 3.1 μM. Together with good repeatability and regeneration, the QCM sensor was also applied to the analysis of copper contamination in drinking water. This work provides a flexible method for fabricating QCM sensors for the analysis of important small molecules in environmental and biological samples.

The photoproducts from reaction of thymine with cysteine, an amino acid containing a sulfhydryl group, have been studied in detail, whereas results of less extensive studies have been reported for the uracil-cysteine system. However, products arising from corresponding reactions of cytosine and related compounds with compounds containing a sulfhydryl group have not been similarly studied. We report here the results of our study of the photoreaction of 5-methylcytosine (5MeCyt), a minor base occurring in mammalian DNA, with 3-mercaptopropionic acid (3MP), a model compound for cysteine. We found that this reaction proceeds at pH 7 to yield N-(N'-(2'-carboxyethyl)thiocarbamoyl)-3-amino-2-methylacrylamidine (Ia) as a primary photoproduct. A secondary thermal product, identified as 3-(2'-carboxyethylthio)-2-methylacrylamidine (IIa), appears if photoreacted solution is allowed to stand for appreciable times prior to workup; this latter compound is formed via an intermediate product. Heating of purified Ia at 100°C or standing at lower temperatures produces 3-amino-2-methylacrylamidine (IId); similarly, irradiation of Ia with UVB light in aqueous solution converts it into IId. Results from exploratory studies suggest that 5MeCyt similarly reacts with other thiols (2-mercaptoethanol, 2-mercaptoacetic acid) to form analogs of Ia and IIa. Other preliminary results suggest that 5-methyl-2'-deoxycytidine and 1,5-dimethylcytosine photoreact with 3MP to form compounds similar to Ia., (© 2013 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2013 The American Society of Photobiology.)

Object: Over the past 20 years, endovascular embolization has become the preferred method of treating cerebral aneurysms. While there are many embolic devices on the market, none is ideal. In this study the authors investigated the use of a liquid-to-solid gelling polymer system-that is, poly(propylene glycol) diacrylate and pentaerythritol tetrakis (3-mercaptopropionate) (PPODA-QT)-to embolize in vivo aneurysms over a 6-month period., Methods: Experimental aneurysms were created in the carotid arteries of 9 canines. Aneurysms were embolized with the polymer only (PPODA-QT, 3 dogs), filled with PPODA-QT after placement of a "framing" platinum coil (coil+PPODA-QT, 3 dogs), or packed with platinum coils (coils only, 3 dogs). Aneurysm occlusion was angiographically monitored immediately and 6 months after embolization. After 6 months, the ostial regions of explanted aneurysms were assessed macroscopically and histologically., Results: All aneurysms showed 100% angiographic occlusion at 6 months, but turbulent blood flow was observed in 1 coils-only sample. Ostial regions of explanted coils-only aneurysms showed neointimal tissue surrounding individual coils but no continuous tissue layer over the aneurysm neck. All PPODA-QT aneurysms displayed smooth ostial surfaces, but 2 of 3 coil+PPODA-QT aneurysms showed polymer (unassociated with the coil) protruding into the vessel lumen, contributing to rough ostial surfaces. Neointimal tissue was present in PPODA-QT and coil+PPODA-QT aneurysms and covered smooth ostial surfaces more completely than in coils-only aneurysms., Conclusions: This study compared neointimal tissue overgrowth in the ostium of experimental aneurysms embolized with PPODA-QT, PPODA-QT plus a framing coil, or coils alone. The coils-only and coil+PPODA-QT groups showed rough and discontinuous ostial surfaces, which hindered neointimal tissue coverage. The PPODA-QT aneurysms consistently produced smooth ostial surfaces that facilitated more complete neointimal tissue coverage over aneurysm necks.

The field of light-emitting nanoparticles has experienced an enormous development over the past two decades. The fluorescence of these nanometer-size crystalline particles, called quantum dots (QDs), can be both quenched and enhanced by different compounds. Since a high percentage of articles related to QDs are focused on theoretical studies, the development of analytical methods with real applications is an important step in order to progressively demonstrate the versatility of these particles. Moreover, taking into account that most of the QDs-based analytical methods are non-automated, the development of automated flow methodologies is still a field that presents an important analytical potential. With this purpose, two automatic methodologies, multicommutated flow injection analysis and sequential injection analysis, have been here applied to the analysis of quinolones in pharmaceutical formulations, making use of the quenching effect caused by the analytes over mercaptopropionic acid-capped CdTe QDs fluorescence. Both methodologies were compared in terms of versatility, sample throughput, sensitivity, etc., and applied to the determination of five quinolones in pharmaceutical preparations available in the Spanish Pharmacopoeia. The detection limits ranged between 26 and 50μmolL(-1), and Relative Standard Deviations lower than 3% were observed in all cases., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In recent years, the number of scientific papers regarding the use of quantum dots (QDs) has increased almost exponentially, especially emphasizing their use for new applications and describing new approaches. One of the future trends in the development of new methods of analysis is the use of automated methodologies. Among them, Multicommutated Flow Injection Analysis has been here selected in order to show its potentiality in pharmaceutical and food analysis. Using water-soluble CdTe QDs modified by mercaptopropionic acid, a flow system was developed for the determination of ascorbic acid. The system was based on the quenching effect produced by ascorbic acid on the fluorescence of QDs. Under the optimized conditions, the relationship between the fluorescence intensity of the QDs and ascorbic acid concentration was linear in the range of 12-250 μg mL(-1), obtaining a sample throughput of 68 determinations per hour. The proposed method was applied to the determination of ascorbic acid in pharmaceutical formulations, goji capsules and fruit juices. The results obtained were in good agreement with those showed by a reference method, so indicating the utility of the proposed method in the clinical and alimentary fields., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In order to construct a three-dimensional electrode, in situ electrochemical deposition of gold nanoparticles onto a gold electrode coated with a self-assembled monolayer of 3-mercaptopropionic acid (Au NP/MPA/Au) was conducted. Horseradish peroxidase (HRP) was then immobilized into this three-dimensional electrode, leading to the realization of direct electron transfer of HRP. Scanning electron microscopy and electrochemical impedance spectroscopy were applied to characterize the electrode before and after HRP immobilization. The apparent Michaelis-Menten constant for immobilized HRP on a Au NP/MPA/Au electrode is 0.78 mM, indicating high enzymatic activity of HRP. The HRP modified electrode was further utilized as a sensing platform for the electrocatalytic reduction and detection of hydrogen peroxide. For the detection of hydrogen peroxide on this electrode, the sensitivity is 311.72 μA mM(-1) cm(-2), the detection limit is 0.16 μM, and the dynamic range is from 0.48 μM to 1.2 mM. Therefore this electrode is a promising device for sensitive and reproducible detection of H(2)O(2)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Synthetic, hydrolytically degradable biomaterials have been widely developed for biomedical use; however, most of them will form acidic products upon degradation of polymer backbone. In order to address this concern, we proposed to fabricate a biodegradable gel based on the crosslinking of a cyclic acetal monomer with reactable diallyl group and multifunctional thiols by thiol-ene photopolymerization. This gel produces diols and carbonyl end groups upon hydrolytic degradation and could be entirely devoid of acidic by-products. Real time infrared spectroscopy was employed to investigate the effect of different light intensities and concentrations of photoinitiator on the polymerization kinetics. With the increase of the concentration of photoinitiator and light intensity, both the rate of polymerization and final double bond conversion increased. Degradation of cyclic acetal based networks was investigated in PBS medium so as to simulate physiological conditions. The remaining mass of the materials after 25 days incubation was 84%. TGA analysis showed that the gels exhibited a typical weight loss (97.2%) at around 378 °C. In vitro cytotoxicity showed that the cyclic acetal based gels had non-toxicity to cell L-929 and had good biocompatibility., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Density functional theory was applied to study the interaction of group IIb transition-metal cations (Zn(2+), Cd(2+), and Hg(2+)) with one and two fully or partially deprotonated 3-mercaptopropionic acid ligands. In this investigation, we determined the geometries of all possible complexes resulting from the coordination of the metal ions with the ligands at different binding sites selected on each ligand. The relative energies of the complexes, metal-ion affinities, free energies, and entropies were also determined. The natures of the bonds were critically analyzed by natural bond orbital (NBO) analysis and clarified further using the atoms-in-molecules (AIM) approach. The substantial influence of the solvent (water) polarization on the energetics, geometries, and bonding of the molecular complexes was also investigated by the conductor-like screening solvation model (COSMO). In an attempt to simulate the complexes in an aqueous environment, water molecules were added explicitly to complete the coordination sphere of the metal cations, and the corresponding metal-ion affinities were calculated to study the effect of microhydration.

3MPA-CdTe QDs in aqueous dispersion was used as a fluorescent probe for the determination of lapachol, a natural naphthoquinone found in plants of the Bignoniaceae family genus Tabebuia. Working QDs dispersions (4.5×10(-8) mol L(-1) of QDs) was prepared in aqueous media containing Tris-HCl buffer pH 7.4 and methanol (10% in volume). The excitation was made at 380 nm with signal measurement at 540 nm. To establish a relationship between fluorescence (corrected to inner filter effect) and concentration of lapachol, a Stern-Volmer model was used. The linear range obtained was from 1.0×10(-5) to 1.0×10(-4) mol L(-1). The limit of detection (x(b)-3s(b)) was 8.0×10(-6) mol L(-1). The 3MPA-CdTe QDs probe was tested in the determination of lapachol in urine, previously cleansed in an acrylic polymer. The average recovery was satisfactory., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The conformation change of bovine hemoglobin (Hb) during the unfolding process induced by urea and acid was investigated by an electrochemical method. Hb unfolding induced by urea of different concentrations was realized by bonding Hb onto a 3-mercaptopropionic acid (MPA) modified gold electrode. The difference in unfolding percentage showed that the Hb unfolding induced by urea was a two-step, three-state transition process, while the unfolding induced by acid was a two-state transition process. The results obtained by the electrochemical method coincided closely with those obtained by UV-vis spectroscopy and fluorescence spectroscopy. Some thermodynamic parameters during the conformational change were also calculated to study the intermediate state during the Hb unfolding process. The present work may lead to an easy and effective way to study metalloproteins unfolding, and holds great promise for the design of novel sensitive biosensors.

Hydroxytyrosol (HXT) has been reported to have beneficial effects for human health, such as antioxidant and antimicrobial properties and an important contribution to the prevention of cardiovascular disease. Hence, exhaustive research is currently being performed to prepare functional foods, such as tomato juice or milk, with HXT. This paper presents a multi-commutated flow method based on the quenching effect that HXT has on the fluorescence of water-soluble mercaptopropionic acid-capped CdTe quantum dots. Under optimal conditions a linear working range was obtained for concentrations between 10 and 250 ng µl⁻¹. In order to demonstrate the suitability of the proposed method for the determination of HXT, HXT-enriched samples were prepared. Using a QuEChERS (quick, easy, cheap, effective, rugged and safe) procedure for extraction, HXT was determined in the prepared functional foods (milk, infant formula, tomato juice and tomato soup). Recoveries of 100% ± 8%, relative standard deviations (RSDs) lower than 5% and high sample throughput of 70 samples per h show the potential of the system for the analysis of HXT in food samples.

Mercaptopropionic acid (MPA) capped CdTe quantum dots (QDs) with particle size 3 nm have been successfully synthesized in aqueous medium by hydrothermal synthesis method. And the effects of different metal ions on MPA capped CdTe QDs fluorescence were studied using fluorescence spectrometry. The results demonstrated that at the same concentration level, Ag(+) could strongly quench CdTe QDs fluorescence, and the other metal ions had little effect on CdTe QDs fluorescence except Cu(2+). On the basis of this fact, a rapid, simple, highly sensitive and selective method based on fluorescence quenching principle for Ag(+) detection in aqueous solution was proposed. Under optimal conditions, the quenched fluorescence intensity (F(0)-F) increased linearly with the concentration of Ag(+) ranging from 4 × 10(-7) to 32 × 10(-7)mol L(-1). The limit of detection for Ag(+) was 4.106 × 10(-8)mol L(-1). The obtained plot of F(0)/F versus [Ag(+)] was an upward curvature, concave towards the y-axis, rather than a straight line. The modified form of the Stern-Volmer equation was third order in Ag(+) concentration. According to the modified Stern-Volmer equation, it can be inferred that dynamic quenching and static quenching simultaneously occurred when Ag(+) interacted with MPA capped CdTe QDs. At the same time other factors might also influence the quenching process. Based on this study, hydrothermal synthesized MPA capped CdTe QDs with particle size 3 nm may be used as a novel fluorescence probe to quantificationally and selectively detect Ag(+)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

3-Mercaptopropionic acid (MPA) capped ZnS nanocrystals (ZnS(MPA)) are covalently attached to a self assembled monolayer (SAM) of 3-aminopropyltriethoxysilane (APTES) on an indium-tin-oxide (ITO) coated glass plate. The protein antibody, anti-myoglobin (Ab-Mb), is covalently linked to free carboxyl groups present on ZnS(MPA) nanocrystals via carbodiimide coupling reaction to form a bioelectrode (Ab-Mb(BSA)/ZnS(MPA)/APTES/ITO-glass). This bioelectrode has been characterized using atomic force microscopy (AFM), contact angle measurements, cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The optimal equivalent circuit model that matches the impedimetric responses of the bioelectrode describes three distinct regions: the electrolyte solution resistance (R(s)), the double layer capacitance (C(dl)) and the specific charge transfer resistance (R(et)). The EIS measurements revealed that the R(et) increases considerably with no significant change in C(dl) after immunoreaction with protein specific antigen myoglobin, Ag-Mb, so that the prepared bioelectrode can be used for the detection of Ag-Mb. The bioelectrode exhibits an electrochemical impedance response to Ag-Mb, in a linear range from 10ng to 1μgmL(-1) phosphate buffer solution (pH 7.4) with a R(et) sensitivity of 117.36Ωcm(2) per decade., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Semiconductor quantum dots (QD) have been widely used for fluorescent bioimaging. However their biosafety has attracted increasing attention, since the data about their in vivo behavior in biological systems are still limited. In this paper we have investigated the short- and long-term biodistribution of intact fluorescent CdSe/CdS/ZnS QD coated by 3-mercaptopropionic acid in mice. The results showed that intravenously injected QD accumulated mainly in the lungs, liver and spleen and were retained in these tissues for over 22 days. QD caused signs of acute toxicity in mice including death. The investigated QD possibly caused vascular thrombosis. The results of a toxicological assay indicated that some histopathological changes occurred in the lung tissue after the injection of QD. Our study highlights the need for careful evaluation of QD safety before their use in biological applications., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A strong ligand effect was observed for the aqueous-phase growth of ZnSe quantum dots (QDs) in the Ostwald ripening (OR) stage. The QDs were made by injecting Se monomer at room temperature followed by a ramp to 100 °C. The ramp produced a second, more gradual increase in the concentrations of both Zn and Se monomers fed by the dissolution of QDs below the critical size. The dissolution process was followed using measurements of the mass of Zn in QDs and in the supernatant by inductively coupled plasma optical emission spectroscopy (ICP-OES). Despite the flux of monomers, there was little growth in the QDs of average size based on UV-vis absorption spectra, until the temperature reached 100 °C, when there was a period of rapid growth followed by a period of linear growth. The linear growth stage is the result of OR as the total mass of Zn in QDs and in the solvent remained constant. The growth data were fit to a continuum model for the limiting case of surface reaction control. The rate is proportional to the equilibrium coefficient for ligand detachment from the QD surface. The ligand 3-mercaptopropionic acid (MPA) was the most tightly bound to the surface and produced the lowest growth rate of (1.5-2) × 10(-3) nm/min in the OR stage, whereas thiolactic acid (TLA) was the most labile and produced the highest growth rate of 3 × 10(-3) nm/min. Methyl thioglycolate (MTG) and thioglycolic acid (TGA) produced rates in between these values. Ligands containing electron-withdrawing groups closer to the S atom and branching promote growth, whereas longer, possibly bidendate, ligands retard it. Mixed ligand experiments confirmed that growth is determined by ligand bonding strength to the QD. Photoluminescence spectroscopy showed that the more labile the ligand, the more facile the repair of surface defects during the exposure of the QDs to room light.

Cadmium selenium (CdSe) quantum dots (QDs) are semiconductor nanocrystals that hold wide range of applications and substantial production volumes. Due to unique composition and nanoscale properties, their potential toxicity to aquatic organisms has increasingly gained a great amount of interest. However, the impact of CdSe QDs exposure on zebrafish embryo and larvae remains almost unknown. Therefore, the lab study was performed to determine the developmental and behavioral toxicities to zebrafish under continuous exposure to low level CdSe QDs (0.05-31.25 mg L(-1)) coated with mercaptopropionic acid (MPA). The results showed MPA-CdSe exposure from embryo to larvae stage affected overall fitness. Our findings for the first time revealed that: (1) The 120 h LC(50) of MPA-CdSe for zebrafish was 1.98 mg L(-1); (2) embryos exposed to MPA-CdSe resulted in malformations incidence and lower hatch rate; (3) abnormal vascular of FLI-1 transgenic zebrafish larvae appeared after exposure to MPA-CdSe including vascular junction, bifurcation, crossing and particle appearance; (4) larvae behavior assessment showed during MPA-CdSe exposure a rapid transition from light-to-dark elicited a similar, brief burst and a higher basal swimming rate; (5) MPA-CdSe induced embryos cell apoptosis in the head and tail region. Results of the observations provide a basic understanding of MPA-CdSe toxicity to aquatic organisms and suggest the need for additional research to identify the toxicological mechanism., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

We report on the microstructural crystal phase transformation of electrospun TiO(2) nanofibers generated via sol-gel electrospinning technique, and the incorporation of as-synthesized CdSe quantum dots (QDs) to different phases of TiO(2) nanofibers (NFs) via bifunctional surface modification. The effect of different phases of TiO(2) on photo-excited electron injection from CdSe QDs to TiO(2) NFs, as measured by photoluminescence spectroscopy (PL) is also discussed. Nanofiber diameter and crystal structures are dramatically affected by different calcination temperatures due to removal of polymer carrier, conversion of ceramic precursor into ceramic nanofibers, and formation of different TiO(2) phases in the fibers. At a low calcination temperature of 400 (o)C only anatase TiO(2) nanofiber are obtained; with increasing calcination temperature (up to 500 (o)C) these anatase crystals became larger. Crystal transformation from the anatase to the rutile phase is observed above 500(o)C, with most of the crystals transforming into the rutile phase at 800(o)C. Bi-functional surface modification of calcined TiO(2) nanofibers with 3-mercaptopropionic acid (3-MPA) is used to incorporate as-synthesized CdSe QD nanoparticles on to TiO(2) nanofibers. Evidence of formation of CdSe/TiO(2) composite nanofibers is obtained from elemental analysis using Energy Dispersive X-ray spectroscopy (EDS) and TEM microscopy that reveal templated quantum dots on TiO(2) nanofibers. Photoluminescence emission intensities increase considerably with the addition of QDs to all TiO(2) nanofiber samples, with fibers containing small amount of rutile crystals with anatase crystals showing the most enhanced effect.

We report photocatalytic H(2) production by hydrogenase (H(2)ase)-quantum dot (QD) hybrid assemblies. Quenching of the CdTe exciton emission was observed, consistent with electron transfer from the quantum dot to H(2)ase. GC analysis showed light-driven H(2) production in the presence of a sacrificial electron donor with an efficiency of 4%, which is likely a lower limit for these hybrid systems. FTIR spectroscopy was employed for direct observation of active-site reduction in unprecedented detail for photodriven H(2)ase catalysis with sensitivity toward both H(2)ase and the sacrificial electron donor. Photosensitization with Ru(bpy)(3)(2+) showed distinct FTIR photoreduction properties, generating all of the states along the steady-state catalytic cycle with minimal H(2) production, indicating slow, sequential one-electron reduction steps. Comparing the H(2)ase activity and FTIR results for the two systems showed that QDs bind more efficiently for electron transfer and that the final enzyme state is different for the two sensitizers. The possible origins of these differences and their implications for the enzymatic mechanism are discussed.

Rhodamine 6G (R6G) and 3-mercaptopropionic acid (MPA) capped-CdTe quantum dots (QDs) were conjugated by electrostatic interactions in aqueous solution. The R6G-QDs conjugate was utilized as a photoluminescence (PL) ratiometric sensor for the detection of glutathione (GSH). In this method, intentional introduction of GSH destroyed the conjugation of R6G and QDs, and induced regular PL change of R6G-QDs conjugates due to the competitive chelation between GSH and MPA ligand on the surface of QDs. The ratio of PL intensity of R6G (I(R6G)) to that of QDs (I(QDs)) in this conjugate was near linear toward the concentration of GSH in the range from 0.05 to 80 μM, and corresponding regression equation showed a good linear coefficient of 0.9954. The limit of detection of 15 nM in this proposed method was about 40-fold lower than that of other QDs-based PL sensors. Interferential experiments testified that R6G-QDs conjugates-based ratiometric PL sensor of GSH showed high selectivity over other related thiols and amino acids. Real sample assays further verified perfect analysis performance of the PL sensor of GSH. In comparison with conventional analytical techniques for the measurement of GSH, this ratiometric PL sensor was facile, economic, highly sensitive and selective., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Chemically modified oligonucleotides play a significant role for genomic research. Modified nucleosides, such as with a fluorescent dye, can be obtained by chemical synthesis. Site-specifically modified long nucleic acids are obtained by ligation of chemically modified short oligonucleotides with enzyme, photochemistry, or catalytic DNA. The functionality-transfer ODN (FT-ODN), which contains 2'-deoxy-6-thioguanosine (6-thio-dG) functionalized with the 2-methyliden-1,3-diketone group, is hybridized with the target RNA to trigger the selective functionalization of the 4-amino group of the cytosine base at pH 7 or the 2-amino group of the guanine base at pH 9.4 or at pH 7.4 in the presence of NiCl(2). In particular, the functionality-transfer reaction (FTR) under the alkaline conditions or neutral conditions in the presence of NiCl(2) proceeds rapidly and selectively to lead to the modification of the target guanine. The transfer reaction of the acetylene-containing diketone group produces the acetylene-modified RNA, which can be subjected to the Cu(I)-catalyzed "click chemistry" with a variety of azide compounds for highly specific, internal modification of RNA., (© 2012 by John Wiley & Sons, Inc.)

An aqueous route of synthesis is described for rapid synthesis of lead selenide quantum dots (PbSe QDs) at room temperature in an attempt to produce water-soluble and stable nanocrystals. Several thiol-ligands, including thioglycolic acid (TGA), thioglycerol (TGC), 3-mercaptopropionic acid (MPA), 2-mercaptoethylamine hydrochloride (MEA), 6-mercaptohexanoic acid (MHA), and l-cysteine (l-cys), were used for capping/stabilization of PbSe QDs. The effects of the ligands on the stability of PbSe QDs were evaluated for a period of two months at room temperature under normal light conditions and at 4 °C in the dark. The TGA- and MEA-capped QDs exhibited the highest stability prior to purification, almost two months when kept in the dark at 4 °C. However, the stability of TGA-capped QDs was reduced substantially after purification to about 5 days under the same conditions, while MEA-capped QDs did not show any significant instability. The stabilization energies of Pb-thiolate complexes determined by theoretical DFT simulations supported the experimental results. The PbSe QDs capped with TGA, MPA and MEA were successfully purified and re-dispersed in water, while those stabilized with TGC, MHA and l-cys aggregated during purification attempts. The purified PbSe QDs possess very susceptible surface resulting in poor stability for about 30-45 min after re-dispersion in water. In the presence of an excess of free ligand, the stability increased up to 5 days for TGA-capped QDs at pH 7.19, 9-12 days for MPA-capped QDs at pH 7.3-7.5 and 45-47 days for MEA-capped QDs at pH 7.35. X-Ray diffraction (XRD) results showed that the QDs possess a cubic rock salt structure with the most intense peaks located at 2θ = 25.3° (200) and 2θ = 29.2° (100). TEM images showed that the size of the QDs ranges between 5 and 10 nm. ICP-MS results revealed that Pb : Se ratios were 1.26, 1.28, 3.85, 1.18, and 1.31 for the QDs capped with TGA, MPA, MEA, l-cys, and TGC, respectively. The proposed method is inexpensive, simple and utilizes environmentally friendly chemicals and solvents., (This journal is © The Royal Society of Chemistry 2012)

S-nitrosothiol (RSNO) solutions represent a valuable source of nitric oxide and could be used as topical vasodilators, but their fast decomposition rate poses a serious obstacle to their potentially widespread therapeutic use. Our aim was to characterize and quantify the effect of pH on S-nitrosothiol formation and decomposition in simple aqueous solutions of S-nitrosoglutathione (GSNO), S-nitroso-N-acetylcysteine (SNAC) and S-nitroso-3-mercaptopropionic acid (SN3MPA). Furthermore, we investigated the effect of storage pH on the stability of GSNO incorporated in poly(ethylene glycol)/ poly(vinyl alcohol) matrices. S-nitrosothiol concentrations were measured spectrophotometrically and laser Doppler scanning method was used to assess dermal blood flow. GSH and NAC solutions reached a complete transformation to nitrosothiols when synthesized using acidic NaNO(2) solution. The initial concentration of all investigated RSNOs decreased more slowly with pH adjusted to mildly basic values (8.4-8.8) for the storage period. Polymer gels of PVA/PEG compositions at mildly basic storage pH further reduced the decomposition rate succeeding to contain 46.8% of the initial GSNO concentration for 25 days. This amount of topically administered GSNO was still capable of increasing the dermal blood flow over 200% in human subjects.

Aiming to find an alternative electrochemiluminescence (ECL) quenching route of high efficiency, biocatalytic precipitation (BCP) was firstly coupled with ECL for investigating its insulating effect on ECL. Experimental data revealed that an insulating layer could be formed via BCP onto the electrode surface, inhibiting the reaction between the coreactant and luminophore and thereby impairing the ECL emission dramatically. Since the extent of insulating effect associated strongly with analyte concentration, a new ECL biosensor was successfully realized. In a model horseradish peroxidase (HRP)-based system, the fabricated biosensor possessed high sensitivity and wide linear range from 1.0 × 10(-10)M to 1.0 × 10(-6)M for H(2)O(2) determination with a detection limit of 4 × 10(-11)M (S/N=3). This method has great potential in extending the application of ECL biosensor for various bioanalytes., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Water-soluble fluorescent copper, silver and gold nanoclusters with quantum yields of 2.2, 6.8 and 5.3%, respectively, are prepared by a robust photoreduction of their inorganic precursors in the presence of poly (methacrylic acid) functionalized with pentaerythritol tetrakis 3-mercaptopropionate., (This journal is © The Royal Society of Chemistry 2012)

Quantum dots (QDs) show promise as novel nanomaterials for sentinel lymph node (SLN) mapping through their use in noninvasive in vivo fluorescence imaging, and they have provided remarkable results. However, in vivo fluorescence imaging has limitations mainly reflected in the strong autofluorescence and low deepness of tissue penetration associated with this technique. Here, we report on the use of self-illuminating 3-mercaptopropionic acid-capped CdTe/CdS QDs for mouse axillary SLN mapping by bioluminescence resonance energy transfer, which was found to overcome these limitations [corrected]. We used CdTe/CdS QDs synthesized in aqueous solution to conjugate a mutant of the bioluminescent protein, Renilla reniformis luciferase. The nanobioconjugates obtained had an average hydrodynamic diameter of 19 nm, and their luminescence catalyzed by the substrate (coelenterazine) could penetrate into at least 20 mm of hairless pigskin, which could be observed using an in vivo imaging system equipped with a 700 nm emission filter. Conversely, the fluorescence of the nanobioconjugates penetrated no more than 10 mm of pigskin and was observed with a strong background. When 80 μL of the nanobioconjugates (containing about 0.5 μmol/L of QDs) and 5 μL of coelenterazine (1 μg/μL) were intradermally injected into a mouse paw, the axillary SLN could be imaged in real time without external excitation, and little background interference was detected. Furthermore, the decayed luminescence of QD-Luc8 in SLNs could be recovered after being intradermally reinjected with the coelenterazine. Our data showed that using self-illuminating QDs, as opposed to fluorescence QDs, has greatly enhanced sensitivity in SLN mapping, and that the SLN could be identified synchronously by the luminescence and fluorescence of the self-illuminating QDs.

Detailed protocols for the preparation of CdSe nanocrystals coated with a multishell structure of ZnS and their surface modification based on the successive ion layer adsorption and reaction method are described. The first phase of the synthesis produces a hydrophobic surface consisting of a TOPO/HDA ligand mixture. This is followed by a surface modification of the quantum dots (QDs) with 3-mercaptopropionic acid by the phase transfer method. The modified QDs become soluble in aqueous systems such as water or buffers for further biological applications.

Like most of the new technologies designed to interact with biological systems, the applications of -nanomaterials needs a proper assessment for their potential impacts. It is only through addressing the issues raised by toxicological studies that nanotechnology will be able to acquire its full potential. Here, we describe the detailed protocols to study the responses of plant cells to their exposure to nanoparticles, including viability, oxidative stress detection, and reactive oxygen species enzymatic detoxification, as well as particle uptake.

This research investigates the origin of specific molecule-adsorption induced surface-stress for micro/nano-cantilever bio/chemical sensors. Systematic discussion is presented on the contribution from types of molecule interactions to the generated surface-stress sensing signal. With the main arguments verified by our micro-cantilever sensing experiments, the origin of the adsorption induced surface-stress is, for the first time, clearly categorized into interface vertical effects and lateral interactions, which helps to comprehensively understand the surface-stress generation and overall to optimize the sensing performance of micro-cantilever chemo-mechanical sensors. The key findings of this research are that, vertically at the molecule adsorption surface, interfacial energy change and charge redistribution are the main origins of the generated surface-stress. More importantly, intermolecular lateral interactions may make a more significant contribution to the nano-mechanical surface-stress response. Compared with other lateral interactions like van der Waals force and the electrostatic coulombic effect, intermolecular hydrogen-bond intensity and steric factor easily cause much greater disparity in surface-stress.

Quantum dots (QDs) are generally used for the conventional fluorescence detection. However, it is difficult for the QDs to be applied in time-resolved fluorometry due to their short-lived emission. In this paper, high-quality Mn-doped ZnSe QDs with long-lived emission were prepared using a green and rapid microwave-assisted synthetic approach in aqueous solution. Fluorescence lifetime of the Mn-doped ZnSe QDs was extended as long as 400 μs, which was 10,000 times higher than that of conventional QDs such as CdS, CdSe, and CdTe. The QDs exhibited an excellent photostability over 35 h under continuous irradiation at 260 nm. Capped with mercaptopropionic acid (MPA), the Mn-doped ZnSe QDs were used for the time-resolved fluorescence detection of 5-fluorouracil (5-FU) with the detection limit of 128 nM. The relative standard deviation for seven independent measurements of 1.5 μM 5-FU was 3.8%, and the recovery ranged from 93% to 106%. The results revealed that the Mn-doped ZnSe QDs could be a good candidate as a luminescence probe for highly sensitive time-resolved fluorometry.

In this article, we report a method of antibody immobilization carried out by hybridizing DNA-antibody conjugates on a mixed self-assembled monolayer composed of DNA thiols and mercaptopropionic acid via sequence-specific hybridization. The proposed method was applied to fabricate an immunosensor for detecting human immunoglobulin G (IgG). Under the optimized experimental conditions, a wide linear range from 50.0 to 500 μg/ml was reached with a detection limit of 30.13 μg/ml. The developed immunosensor possesses advantages such as simple fabrication, wide linear range, easy regeneration, and excellent reproducibility., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The design of a catalyst for one of the most important electrocatalytic reactions, the oxygen reduction reaction (ORR), was done following the most recent guidelines of theoretical studies on this topic. Aim of this work was to achieve a synergic effect of two different metals acting on different steps of the ORR. The catalytic activity of Ag, already known and characterized, was enhanced by the presence of a monolayer of cobalt subdivided into nanosized islands. To obtain such a controlled nanostructure, a novel method utilizing self-assembled monolayers (SAMs) as templates was employed. In a recent study, we were able to perform a confined electrodeposition of cobalt onto Ag(111) in a template formed by selectively desorbing a short-chain thiol (3-mercaptopropionic acid, MPA) from binary SAMs using 1-dodecanthiols (DDT). This method allows for an excellent control of the morphology of the deposit by varying the molar ratio of the two thiols. Because cobalt does not deposit on silver at an underpotential, the alternative approach of surface limited redox replacement (SLRR) was used. This method, recently developed by Adžić et al., consists of the use of a monolayer of a third metal, which can be deposited at an underpotential, as a template for the spontaneous deposition of a more noble metal. Herein, we choose zinc as template for the deposition of cobalt. Ag(111) crystals were covered by monolayer islands consisting of cobalt, with the surface atomic ratios ranging from 12 to 39% for cobalt. The catalytic activity of such samples towards ORR was evaluated and the best improvement in activity was found to be that of the sample with a cobalt percentage of approximately 30% with respect to the bare silver, which is in good agreement with theoretical hypotheses., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Quantum dots (QDs) nanoprobes are emerging as alternatives to small-molecule fluorescent probes in biomedical technology. This paper reports an efficient and rapid method of producing highly dispersed and stable CdSe-core QDs with a hydrophobic gradient. Amphiphilic core/shell CdSe/ZnS QDs were prepared by ligand exchange at the surface of lipophilic CdSe/ZnS QDs using the dihydrolipoic acid (DHLA) dithiol ligand linked to leucine or phenylalanine amino acids. Contact angle relaxations on a hydrophobic surface and surface tension measurements indicated that aqueous dispersions of CdSe/ZnS@DHLA-Leu or CdSe/ZnS@DHLA-Phe QDs exhibit increased hydrophobicity compared to CdSe-core QDs capped by the hydrophilic 3-mercaptopropionic acid (MPA) ligand. We found that the surface functional groups and the ligand density at the periphery of these QDs significantly dictated their interactions with a complex biological matrix called biofilm. Using fluorescence confocal microscopy and an autocorrelation function (semi-variogram), we demonstrated that MPA-capped QDs were homogeneously associated to the biopolymers, while amphiphilic CdSe/ZnS@DHLA-Leu or CdSe/ZnS@DHLA-Phe QDs were specifically confined allowing identification of hydrophobic microdomains of the biofilms. Results obtained clearly point out that the final destination of QDs in biofilms can properly be controlled by an appropriate design of surface ligands., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

A set of novel apomorphine derivatives were synthesized with diversely functionalized side chains in the proximity of position 2 of the aporphine skeleton. Amino and/or carboxylic functions were introduced to this region of the backbone to test their pharmacological effects. During the synthesis of 2-(S-3-mercaptopropionic acid)-derivative a heteroring-fused congener was also isolated. The structural elucidation confirmed that the formation of this product was in accordance with our previous observations on the reaction of thebaine (2) with thiosalycilic acid. All the novel apomorphine congeners 4a-g were neuropharmacologically characterized to discover their dopaminergic profiles. Two derivatives were identified as D(2) full agonists equipotent with apomorphine (1) having significantly increased D(2)/D(1) selectivity ratios., (Copyright © 2011 Elsevier Masson SAS. All rights reserved.)

Semiconductor quantum dots (QDs) coated with thioalkyl acid ligands are often used as probes and reporters for nucleic acid sensing, or protein sensing using aptamers, and are also potential vectors for gene delivery. In such applications, the interactions that potentially lead to the adsorption of oligonucleotides onto the surface of colloidal QDs are an important consideration. To explore such interactions, fluorescence resonance energy transfer (FRET) between QDs and oligonucleotides labeled with a fluorescent dye was used to identify and characterize a set of conditions that favor strong adsorption on 3-mercaptopropionic acid (MPA)-coated CdSe/ZnS QDs. Adsorption curves and competitive binding experiments were used to determine that the order of affinity for nucleobase adsorption was dC>dA≥dG≫dT. The length of the oligonucleotide sequence was also important, with an 80-mer sequence adsorbing more strongly than its 20-mer analog. Adsorption decreased with increasing pH and corresponded to the ionization of the carboxylic acid groups of the MPA ligands. Increased ionic strength partially offsets ligand ionization and increased the extent of adsorption. The interaction between QDs and oligonucleotides was labile, with increases in adsorption at lower concentrations of oligonucleotide and with an increasing number of oligonucleotides per QD. The results were consistent with a hydrogen-bonding model for adsorption, where neutral thioalkyl acid ligands interact favorably with nucleobases and ionized ligands resist adsorption., (Copyright © 2011 Elsevier Inc. All rights reserved.)

As the number of nanoparticle-based products increase in the marketplace, there will be increased potential for human exposures to these engineered materials throughout the product life cycle. We currently lack sufficient data to understand or predict the inherent nanomaterial characteristics that drive nanomaterial-biological interactions and responses. In this study, we utilized the embryonic zebrafish (Danio rerio) model to investigate the importance of nanoparticle (NP) surface functionalization, in particular as it pertains to nanoparticle stability, on in vivo biological responses. This is a comparative study where two lead sulfide nanoparticles (PbS-NPs) with nearly identical core sizes, but functionalized with either sodium 3-mercaptopropanesulfonate (MT) or sodium 2,3-dimercaptopropanesulfonate (DT) ligand, were used. Developmental exposures and assessments revealed differential biological responses to these engineered nanoparticles. Exposures beginning at 6 h post fertilization (hpf) to MT-functionalized nanoparticles (PbS-MT) led to 100% mortality by 120 hpf while exposure to DT-functionalized nanoparticles (PbS-DT) produced less than a 5% incident in mortality at the same concentration. Exposure to the MT and DT ligands themselves did not produce adverse developmental effects when not coupled to the NP core. Following exposure, we confirmed that the embryos took up both PbS-MT and PbS-DT material using inductively coupled plasma-mass spectrometry (ICP-MS). The stability of the nanoparticles in the aqueous solution was also characterized. The nanoparticles decompose and precipitate upon exposure to air. Soluble lead ions were observed following nanoparticle precipitation and in greater concentration for the PbS-MT sample compared to the PbS-DT sample. These studies demonstrate that in vivo assessments can be effectively used to characterize the role of NP surface functionalization in predicting biological responses.

This study describes a strategy of using zinc selenium quantum dots (ZnSe QDs) modified with 3-mercaptopropionic acid (3-MPA) as the matrix for direct analysis of peptides and proteins from sodium salt solution in surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). The enhancement of detection sensitivity for these biomolecules was due to the adsorption of positively charged peptides or proteins onto the surfaces of negatively charged ZnSe-3MPA QDs via electrostatic interactions resulting in an increase in ionization efficiency for sodium adduct ions ([M+Na](+)). The applicability of the current approach was demonstrated for a variety of peptides, including leucine-enkephalin, methione-enkephalin, HW6, substance P and angiotensin II, and proteins (cytochrome c, myoglobin and lysozyme). Signal intensities of these peptides or proteins can be enhanced by 25-95 times compared with those obtained by LDI-MS in the absence of ZnSe-3MPA QDs. Applying ZnSe-3MPA QDs to serve as the matrix in SALDI-MS is a simple and effective approach for direct analysis of peptide and protein molecules from sodium salt solution without any pretreatment as the peptides and proteins can be successfully detected as sodium adduct ions ([M+Na](+))., (Copyright © 2011 John Wiley & Sons, Ltd.)

A series of thiol-ene generated amphiphilic cross-linked networks was prepared by reaction of alkene-modified Boltorn polyesters (Boltorn-ene) with varying weight percent of 4-armed poly(ethylene glycol) (PEG) tetrathiol (0-25 wt%) and varying equivalents of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) (0-64 wt%). These materials were designed to present complex surface topographies and morphologies, with heterogeneity of surface composition and properties and robust mechanical properties, to serve as nontoxic antibiofouling coatings that are amenable to large-scale production for application in the marine environment. Therefore, a two-dimensional matrix of materials compositions was prepared to study the physical and mechanical properties, over which the compositions spanned from 0 to 25 wt% PEG tetrathiol and 0-64 wt% PETMP (the overall thiol/alkene (SH/ene) ratios ranged from 0.00 to 1.00 equiv), with both cross-linker weight percentages calculated with respect to the weight of Boltorn-ene. The Boltorn-ene components were prepared through the esterification of commercially available Boltorn H30 with 3-butenoic acid. The subsequent cross-linking of the Boltorn-PEG-PETMP films was monitored using IR spectroscopy, where it was found that near-complete consumption of both thiol and alkene groups occurred when the stoichiometry was ca. 48 wt% PETMP (0.75 equiv SH/ene, independent of PEG amount). The thermal properties of the films showed an increase in T(g) with an increase in 4-armed PEG-tetrathiol wt%, regardless of the PETMP concentration. Investigation of the bulk mechanical properties in dry and wet states found that the Young's modulus was the greatest at 48 wt% PETMP (0.75 equiv of SH/ene). The ultimate tensile strength increased when PETMP was constant and the PEG concentration was increased. The Young's modulus was slightly lower for wet films at constant PEG or constant PETMP amounts, than for the dry samples. The nanoscopic surface features were probed using atomic force microscopy (AFM), where it was observed that the surface of the amphiphilic films became increasingly rough with increasing PEG wt%. On the basis of the physicochemical data from the diverse sample matrix, a focused compositional profile was then investigated further to determine the antifouling performance of the cross-linked Boltorn-PEG-PETMP networks. For these studies, a low, constant PETMP concentration of 16 wt% was maintained with variation in the PEG wt% (0-35 wt%). Antifouling and fouling-release activities were tested against the marine alga Ulva. Spore settlement densities were low on these films, compared to that on standards of polydimethylsiloxane and glass., (© 2011 American Chemical Society)

Luminescent quantum dots (QDs) possess unique photophysical properties, which are advantageous in the development of new generation robust fluorescent probes based on Forster resonance energy transfer (FRET) phenomena. Bioconjugation of these QDs with biomolecules create hybrid materials having unique photophysical properties along with biological activity. The present study is aimed at characterizing QD bioconjugates in terms of optical behavior. Colloidal CdTe QDs capped with 3-mercaptopropionic acid (MPA) were conjugated to different proteins by the carbodiimide protocol using N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDC) and a coupling reagent like N-hydroxysuccinimide (NHS). The photoabsorption of these QD-protein bioconjugates demonstrated an effective coupling of electronic orbitals of constituents. A linear variation in absorbance of bioconjugates at 330 nm proportionate to conjugation suggests a covalent attachment as confirmed by gel electrophoresis. A red shift in the fluorescence of bovine serum albumin (BSA) due to conjugation inferred a decrease in Stokes shift and solvent polarization effects on protein. A proportionate quenching in BSA fluorescence followed by an enhancement of QD fluorescence point toward nonradiative dipolar interactions. Further, reduction in photobleaching of BSA suggests QD-biomolecular interactions. Bioconjugation has significantly influenced the photoabsorption spectrum of QD bioconjugates suggesting the formation of a possible protein shell on the surface of QD. The experimental result suggests that these bioconjugates can be considered nanoparticle (NP) superstructures for the development of a new generation of robust nanoprobes.

A sensitive, selective and efficient liquid chromatographic/tandem mass spectrometric (LC/MS/MS) method was developed and validated for the determination of glucosamine in healthy human urine. Urine samples were extracted by acetonitrile and derivatized with o-phthalaldehyde/3-mercaptopropionic acid. Analysis was then carried out using ESI source and methanol/0.2% ammonium acetate-0.1% formic acid mobile phase gradient elution, with tolterodine tartrate as the internal standard. The linear calibration curve ranged from 0.41μg/ml to 82.7μg/ml. The intra-day and inter-day precisions were less than 3.93% and 10.0%, respectively. The extraction recoveries determined at three concentration levels were higher than 88.6%. The method was successfully applied for determining the urine concentration of glucosamine up to 24h after oral administration of 1g glucosamine sulfate dispersible table (containing 785.08mg glucosamine) from a clinical pharmacokinetic study in healthy volunteers., (Published by Elsevier B.V.)