Biomimetic crystallization of unusual macroporous calcium carbonate spherules in the presence of phosphatidylglycerol vesicles

We report the interesting finding that crystallization of calcium carbonate (CaCO3) in the presence of dimyristoylphosphatidylglycerol (DMPG) vesicles by a simple gas diffusion method results in the formation of unusual microscopic CaCO3 spherules. The experimental results indicate that the as-prepared CaCO3 spherules, which have a complex macroporous structure, are predominantly vaterite. It is believed that DMPG vesicles play an important role in the process of crystallization, and the possible formation mechanism is proposed.

Kinetic Study of Prolidase Activity in Erythrocytes against Different Substrates Using Capillary Electrophoresis with Electrochemiluminescence Detection

Capillary electrophoresis (CE) with electrochemiluminescence (ECL) detection was used to explore the kinetics ofthe enzymatic reaction. The different effects ofreaction conditions including the concentration of Mn2l, incubation temperature and pH on PFOlidase (PLD, EC 3.4.13.9) activity in erythrocyte lysates against three different substrates, Gly-Pro, Val-Pro and Leu-Pro were investigated. Also, the effects of colchicine which can prevent or delay cancer ofliver on the PLD activity were studied.

CEC with tris(2,2 '-bipyridyl) ruthenium(II) electrochemiluminescent detection

For the first time, CEC was coupled with tris(2,2-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+) electrochemiluminescence detection. Efficient CEC separations of proline, putrescine, spermidine and spermine were achieved when the pH of the mobile phase is in the range of 3.5-7.0. The optimum mobile phase for CEC separation is much less acidic than that for CZE separation, which matches better with the optimum pH for Ru(bpy)(3)(2+) electrochemiluminescence detection and dramatically shortens the analysis time because of larger EOF at higher pH.

Electrochemiluminescence from tris(2,2 '-bipyridyl)ruthenium(II)-graphene-Nafion modified electrode

An electrochemiluminescence (ECL) sensor based on Ru(bpy)(3)(2+)-graphene-Nafion composite film was developed. The graphene sheet was produced by chemical conversion of graphite, and was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Raman spectroscopy. The introduction of conductive graphene into Nafion not only greatly facilitates the electron transfer of Ru(bpy)(3)(2+), but also dramatically improves the long-term stability of the sensor by inhibiting the migration of Ru(bpy)(3)(2+) into the electrochemically inactive hydrophobic region of Nafion. The ECL sensor gives a good linear range over 1 x 10(-7) to 1 x 10(-4) M with a detection limit of 50 nM towards the determination of tripropylamine (TPA), comparable to that obtained by Nafion-CNT.

Poly[[diaqua-mu-4,4 '-bipyridine-dinitratodi-mu-L-tyrosinato-dicopper(II)]: a chiral two-dimensional coordination polymer

The title compound, [Cu-2(C9H10NO3)(2)(NO3)(2)(C10H8N2)-(H2O)(2)](n), contains Cu-II atoms and L-tyrosinate (L-tyr) and 4,4'-bipyridine (4,4'-bipy) ligands in a 2:2:1 ratio. Each Cu atom is coordinated by one amino N atom and two carboxylate O atoms from two L-tyr ligands, one N atom from a 4,4'-bipy ligand, a monodentate nitrate ion and a water molecule in an elongated octahedral geometry. Adjacent Cu atoms are bridged by the bidentate carboxylate groups into a chain. These chains are further linked by the bridging 4,4'-bipy ligands, forming an undulated chiral two-dimensional sheet. O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds connect the sheets in the [100] direction. This study offers useful information for the engineering of chiral coordination polymers with amino acids and 4,4'-bipy ligands by considering the ratios of the metal ion and organic components.

Sensitive detection of cysteine based on fluorescent silver clusters

In this work,we report the application of novel, water-soluble fluorescent Ag clusters in fluorescent sensors for detecting cysteine, an important biological analyte. The fluorescence of poly(methacrylic acid) (PMAA)templated Ag clusters was found to be quenched effectively by cysteine, but not when the other alpha-amino acids were present. By virtue of the specific response, a new, simple, and sensitive fluorescent method for detecting cysteine has been developed based on Ag clusters. The present assay allows for the selective determination of cysteine in the range of 2.5 x 10(-8) to 6.0 x 10(-6) M with a detection limit of 20 nM at a signal-to-noise ratio of 3. Based on the absorption and fluorescence studies, we suggested that cysteine quenched the emission by the thiol-adsorption-accelerated oxidation of the emissive Ag clusters. The present study shows a promising step toward the application of silver clusters, a new class of attractive fluorescence probes.

Gold nanoparticle-based near-infrared fluorescent detection of biological thiols in human plasma

In this work, a new fluorescent method for sensitive detection of biological thiols in human plasma was developed using a near-infrared (NIR) fluorescent dye, FR 730. The sensing approach was based on the strong affinity of thiols to gold and highly efficient fluorescent quenching ability of gold nanoparticles (Au NPs). In the presence of thiols, the NIR fluorescence would enhance dramatically due to desorption of FR 730 from the surfaces of Au NPs, which allowed the analysis of thiol-containing amino acids in a very simple approach. The size of Au NPs was found to affect the fluorescent assay and the best response for cysteine detection was achieved when using Au NPs with the diameter of 24 nm, where a linear range of 2.5 x 10(-8) M to 4.0 x 10(-6) M and a detection limit of as low as 10 nM was obtained. This method also demonstrated a high selectivity to thiol-containing amino acids due to the strong affinity of thiols to gold.

Sensitive and Selective Sensor for Biothiols in the Cell Based on the Recovered Fluorescence of the CdTe Quantum Dots-Hg(II) System

Herein, a sensitive and selective sensor for biothiols based on the recovered fluorescence of the CdTe quantum dots (QDs)-Hg(II) system is reported. Fluorescence of QDs could be quenched greatly by Hg(II). In the presence of biothiols, such as glutathione (GSH), homocysteine (Hcy), and cysteine (Cys), however, Hg(H) preferred to react with them to form the Hg(II)-S bond because of the strong affinity with the thiols of biothiols rather than quenching the fluorescence of the QDs. Thus, the fluorescence of CdTe QDs was recovered. The restoration ability followed the order GSH > Hcy > Cys due to the decreased steric hindrance effect. A good linear relationship was obtained from 0.6 to 20.0 mu mol L-1 for GSH and from 2.0 to 20.0 mu mol L-1 for Cys, respectively. The detection limits of GSH and Cys were 0.1 and 0.6 mu mol L-1, respectively. In addition, the method showed a high selectivity for Cys among the other 19 amino acids. Furthermore, it succeeded in detecting biothiols in the Hela cell.

Fluorescent conjugated polymer-stabilized gold nanoparticles for sensitive and selective detection of cysteine

We report a new fluorescent detection method for cysteine based on one-step prepared fluorescent conjugated polymer-stabilized gold nanoparticles. The as-prepared fluorescent conjugated polymer-stabilized gold nanoparticles fluoresce weakly due to the fluorescence resonance energy transfer between the fluorophore and the gold nanoparticles. Upon the addition of cysteine, a thiol-containing amino acid, the fluorescence of the colloidal solution increases significantly, indicating that cysteine can modulate the energy transfer between fluorophore and gold. This phenomenon then allows for sensitive detection of cysteine with a limit of detection (LOD) of 25 nM. The linear range of determination of cysteine is from 5 x 10(-8) to 4 x 10(-6) M. None of the other amino acids found in proteins interferes with the determination. Moreover, due to the excellent protecting ability of the fluorescent conjugated polymers, the synthesis of metal nanoparticles and modifying with fluorophores can be accomplished within one step, which makes our method much simpler than conventional methods. We also expect that it will be possible to detect other biologically important analytes based on the fluorescent conjugated polymer-stabilized metal nanoparticles.

One-step synthesis of Ru(2,2 '-bipyridine)(3)Cl-2-immobilized silica nanoparticles for use in electrogenerated chemiluminescence detection

One-step synthesis of Ru (bpy)(3) Cl-2-immobilized (bpy = 2,2'-bipyridine) silica nanoparticles (Ru-silica nanoparticles) for use in electrogenerated-chemiluminescence (ECL) detection is reported. Ru-silica nanoparticles are prepared by using the Stober method. Compared with free Ru(bpy)(3)Cl-2, Ru-silica nanoparticles are seen to exhibit a red-shift of the UV-vis absorbance peak and a longer fluorescence lifetime, which are attributed to the electrostatic interaction of Ru(bpy)(3)(2+) and silica. Because silica nanoparticles are used as immobilization matrices, the surfaces of Ru-silica nanoparticles are easily modified or functionalized via the assembly of other nanoparticles, such as Au. For ECL detection, Au-colloid-modified Ru-silica nanoparticles are immobilized on a 3-mercaptopropyl-trimethoxysilane-modified indium tin oxide electrode surface by Au-S interaction; the surface concentration of electroactive Ru(bpy)(3)Cl-2 is obviously higher than that in silica films.

Adaptive recognition of small molecules by nucleic acid aptamers through a label-free approach

We report a novel label-free method for the investigation of the adaptive recognition of small molecules by nucleic acid aptamers using capillary electrophoresis analysis. Cocaine and argininamide were chosen as model molecules, and the two corresponding DNA aptamers were used. These single-strand DNAs folded into their specific secondary structures, which were mainly responsible for the binding of the target molecules with high affinity and specificity. For molecular recognition, the nucleic acid structures then underwent additional conformational changes, while keeping the target molecules stabilized by intermolecular hydrogen bonds. The intrinsic chemical and physical properties of the target molecules enabled them to act as indicators for adaptive binding. Thus any labeling or modification of the aptamers or target molecules were made obsolete. This label-free method for aptamer-based molecular recognition was also successfully applied to biological fluids and therefore indicates that this approach is a promising tool for bioanalysis.

Nucleation and growth of glycine crystals with controllable sizes and polymorphs on Langmuir-Blodgett films

Control of crystal polymorph and size is very important in many application fields. Herein we demonstrate that Langmuir-Blodgett (LB) films of stearic acid (SA) and octadecylamine (ODA) can serve as templates and generate different polymorphs of glycine crystals. In the neutral aqueous solutions, gamma-glycine crystallizes on LB films of ODA while the polymorphic outcome becomes the (x-form on LB films of SA. These observed results could be explained by the electrostatic interactions and geometric lattice matching at the LB film/crystal interfaces, respectively. By keeping the appropriate supersaturation, we have successfully controlled the number of crystals grown on LB films; for example, in some certain cases, only one piece of crystal was grown on LB films in solution. Therefore, large crystals of centimeter size could be prepared. These experimental results suggest a new approach to produce an organic crystal with bulk scale.

Determination of atenolol and metoprolol by capillary electrophoresis with Tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescence detection

Capillary electrophoresis (CE) coupling with a tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) detection technique was developed for the analysis of two 8-blockers, atenolol (AT) and metoprolol (ME). The parameters that influence the separation and detection, including the buffer pH and concentration, the separation voltage, the detection potential and Ru(bpy)(3)(2+) concentration, were optimized in detail. The calibration curve was linear over a concentration range of two or three orders of magnitude for the two beta-blockers. The detection limits for AT and ME were 0.075 and 0.005 mu M (S/N = 3). The relative standard deviations (n = 8) of the ECL intensity and the migration time were 2.65 and 0.22% for AT, 2.82 and 0.34% for ME, respectively. The proposed method was applied to determine AT and ME in spiked urine samples; satisfactory results were obtained.

Metabolic profiling of serum from gadolinium chloride-treated rats by H-1 NMR spectroscopy

Metabolic profiling of serum from gadolinium chloride (GdCl3, 10 and 50 mg/kg body weight, intraperitoneal [i.p.])-treated rats was investigated by the NMR spectroscopic-based metabonomic strategy. Serum samples were collected at 48, 96, and 168 h postdose (p.d.) after exposure to GdCl3. H-1 NMR spectra of serum were analyzed by pattern recognition using principal components analysis. The studies showed that there was a dose-related biochemical effect of GdCl3 treatment on the levels of a range of low-molecular weight compounds in serum. The liver damage induced by GdCl3 was characterized by the elevation of lactate, pyruvate, and creatine as well as the decrease of branched-chain amino acids (valine and isoleucine), alanine, glucose, and trimethylamine-N-oxide concentration in serum samples. The biochemical effects of GdCl3 in rats could be consulted when evaluating the biochemical profile of gadolinium-containing compounds that are being developed for nuclear magnetic resonance imaging.

Drug-human serum albumin binding studied by capillary electrophoresis with electrochemiluminescence detection

A new technique for investigating drug-protein binding was developed employing capillary electrophoresis (CE) coupled with tris(2,2'-bipyridyl) ruthenium(II) [Ru(bPY)(3)(2+)] electrochemiluminescence (ECL) (CE-ECL) detection after equilibrium dialysis. Three basic drugs, namely pridinol, procyclidine and its analogue trihexyphenidyl, were successfully separated by capillary zone electrophoresis with end-column Ru(bPY)(3)(2+) ECL detection. The relative drug binding to human serum albumin (HSA) for each single drug as well'as for the three drugs binding simultaneously was calculated. It was found that the three antiparkinsonian drugs compete for the same binding site on HSA. This work demonstrated that Ru(bPY)(3)(2+) CE-ECL can be a suitable technique for studying drug-protein binding.