Inner filter effect (IFE) as a simple and selective sensing platform for detection of tetracycline using milk-based nitrogen-doped carbon nanodots as fluorescence probe

A simple, selective, and sensitive turn-off fluorescent assay for detecting of tetracycline in pharmaceutical dosage form based on inner filter effect (IFE) sensing platform has been described. In this IFE sensing strategy, N-doped carbon dots (CDs) were prepared by one-pot solvothermal synthesis using milk as a precursor and were directly used as a fluorophore in IFE. The prepared CDs were characterized by common spectroscopic and microscopic techniques. The CDs exhibited excitation-wavelength dependent emission with 10% as the fluorescence quantum yield. The fluorescence of CDs was decreased in correlation to the addition of absorber (tetracycline), as the excitation spectrum of the fluorophore (CDs) matches the absorption spectrum of the absorber. The present IFE-based sensing platform showed a good linear relationship from 2.0 µM to 200 µM (R² = 0.9960) and provided a detection limit of 0.6 µM (signal-to-noise ratio of 3). Additionally, the cytotoxic effects of CDs were determined using normal healthy male Balb/C mice model treated with various doses of CDs and at the end of the study, no mortality or even no sign of toxicity was observed at oral doses of 100 and 200 mg/kg CDs in all treated animals. The proposed nanoprobe assay is a free from interferences, low-cost, biocompatible, and accurate for the detection of tetracycline in pharmaceutical formulation.     

A novel sensing platform using aptamer and RNA polymerase-based amplification for detection of cancer cells

Cancer is one of the most serious and lethal diseases around the world. Its early detection has become a challenging goal. To address this challenge, we developed a novel sensing platform using aptamer and RNA polymerase-based amplification for the detection of cancer cells. The assay uses the aptamer as a capture probe to recognize and bind the tumor marker on the surface of the cancer cells, forming an aptamer-based sandwich structure for collection of the cells in the microplate wells, and uses SYBR Green II dye as a tracer to produce strong fluorescence signal. The tumor marker interacts first with the recognition probes which were composed of the aptamer and single-stranded T7 RNA polymerase promoter. Then, the recognition probe hybridized with template probes to form a double-stranded T7 RNA polymerase promoter. This dsDNA region is extensively transcribed by T7 RNA polymerase to produce large amounts of RNAs, which are easily monitored using the SYBR Green II dye and a standard fluorometer, resulting in the amplification of the fluorescence signal. Using MCF-7 breast cancer cell as the model cell, the present sensing platform showed a linear range from 5.0 × 10² to 5.0 × 10⁶ cells mL⁻¹ with a detection limit of 5.0 × 10² cells mL⁻¹. This work suggested a strategy to use RNA signal amplification combining aptamer recognition to develop a highly sensitive and selective method for cancer cells detection.     

The separation of gold by selective extraction of HAuBr(4) using a poly(tetramethylene) ether glycol impregnated filter

The separation of gold(III) by selective extraction on an organic- impregnated filter (OIF) was studied. Gold was found to be rapidly extracted into the active polytetramethylene ether glycol (polyTHF) layer of the filter from strongly acidic solutions of HBr, as the HAuBr(4) complex. Quantitative extraction of gold from solution was obtained with flow rates up to 600 ml min(-1) through the 10.75 cm(2) OIF and at ng ml(-1) concentration levels. The extraction is shown to be dependent on the solution flow rate and HBr concentration as well as the filter pore size, thickness and porosity. Gold can be eluted from the filter by converting it into the AuBr(4)(-) complex using a KBr solution. The separation of gold is demonstrated from simple binary metal mixtures involving iron and cadmium, as well as from a more complicated matrix, gold ore solution.     

Solid silica sulfuric acid (SSA) as a novel and efficient catalyst for acetylation of aldehydes and sugars

Acetylation of aldehydes and sugars catalyzed by solid silica sulfuric acid (SSA) is described. In these reactions SSA shows a highly catalytic nature: easy to handle procedure, short reaction time, recycle exploitation, insensitivity to air and moisture, excellent isolated yields. The catalyst could be recycled at least five times.     

A novel fluorescent aptasensor for thrombin detection: using poly(m-phenylenediamine) rods as an effective sensing platform

In this communication, we develop a novel fluorescent aptasensor for thrombin detection with the use of poly(m-phenylenediamine) (PMPD) rods as an effective sensing platform. This aptasensor exhibits extraordinarily high sensitivity with a detection limit as low as 100 pM and excellent selectivity.     

The separation of platinum and palladium by selective extraction of H(2)Pt(SCN)(6) and H(2)Pd(SCN)(4) using a polyTHF-impregnated filter

Platinum and palladium are known to form complexes with the thiocyanate ion in solution. The isolation and separation of both platinum and palladium as thiocyanate complexes is demonstrated by passing them through an organic-impregnated filter (OIF) prepared with polyTHF. Simultaneous extraction is performed by converting both metals into the extractable form. Sequential extraction is achieved by exploiting the difference in the rates of formation for the extractable complexes of the two metals. The extraction of both metals is rapid with quantitative recoveries of platinum with flow rates as high as 600 ml min⁻¹ in small samples, while recoveries from larger volume samples were considerably lower. Once extracted, the metals can be removed from the OIF by conversion to a non-extractable form with a high pH eluting solution. The rapid separation, isolation and preconcentration of both platinum and palladium from aqueous samples is demonstrated.     

Human genomic DNA analysis using a semi-automated sample preparation, amplification, and electrophoresis separation platform

The growing importance of analyzing the human genome to detect hereditary and infectious diseases associated with specific DNA sequences has motivated us to develop automated devices to integrate sample preparation, real-time PCR, and microchannel electrophoresis (MCE). In this report, we present results from an optimized compact system capable of processing a raw sample of blood, extracting the DNA, and performing a multiplexed PCR reaction. Finally, an innovative electrophoretic separation was performed on the post-PCR products using a unique MCE system. The sample preparation system extracted and lysed white blood cells (WBC) from whole blood, producing DNA of sufficient quantity and quality for a polymerase chain reaction (PCR). Separation of multiple amplicons was achieved in a microfabricated channel 30 microm x 100 microm in cross section and 85 mm in length filled with a replaceable methyl cellulose matrix operated under denaturing conditions at 50 degrees C. By incorporating fluorescent-labeled primers in the PCR, the amplicons were identified by a two-color (multiplexed) fluorescence detection system. Two base-pair resolution of single-stranded DNA (PCR products) was achieved. We believe that this integrated system provides a unique solution for DNA analysis.     

Highly sensitive and selective detection of silver(I) ion using nano-C60 as an effective fluorescent sensing platform

In this Communication, we report water-soluble nano-C(60) in the first use as an effective fluorescent sensing platform for the highly sensitive and selective detection of Ag(+). The general concept used in this approach is based on a fluorescently labeled single-stranded DNA (ssDNA) probe that adsorbs on nano-C(60), leading to substantial dye fluorescence quenching; however, in the presence of Ag(+), C-Ag(+)-C coordination induces the probe to fold into a hairpin structure, which does not adsorb on nano-C(60) and thus retains the dye fluorescence. This sensing system exhibits a detection limit as low as 1 nM and has a high selectivity against other metal ions. Finally and most importantly, we demonstrate its performance in real sample analysis.     

Two-electron redox chemistry at the dinuclear core of a TePt platform: chlorine photoreductive elimination and isolation of a Te(V)Pt(I) complex

As part of our interest in novel redox-active main group/transition metal platforms for energy applications, we have synthesized the chloride salt of [Te(III)Pt(I)Cl(o-dppp)(2)](+) ([1](+), o-dppp = o-(Ph(2)P)C(6)H(4)) by reaction of the new bis(phosphino) telluroether (o-(Ph(2)P)C(6)H(4))(2)Te with (Et(2)S)(2)PtCl(2). Complex [1](+) is chemically robust and undergoes a clean two-electron oxidation reaction in the presence of PhICl(2) to afford ClTe(III)Pt(III)Cl(3)(o-dppp)(2) (2), a complex combining a hypervalent four-coordinate tellurium atom and an octahedral platinum center. While the Te-Pt bond length is only slightly affected by the oxidation state of the TePt platform, DFT and NBO calculations show that this central linkage undergoes an umpolung from Te→Pt in [1](+) to Te←Pt in 2. This umpolung signals an increase in the electron releasing ability of the tellurium center upon switching from an eight-electron configuration in [1](+) to a hypervalent configuration in 2. Remarkably, the two-electron redox chemistry displayed by this new dinuclear platform is reversible as shown by the photoreductive elimination of a Cl(2) equivalent when 2 is irradiated at 350 nm in the presence of a radical trap such as 2,3-dimethyl-1,3-butadiene. This photoreductive elimination, which affords [1][Cl] with a maximum quantum yield of 4.4%, shows that main group/late transition metal complexes can mimic the behavior of their transition metal-only analogues and, in particular, undergo halogen photoelimination from the oxidized state. A last notable outcome of this study is the isolation and characterization of F(MeO)(2)Te(V)Pt(I)Cl(o-dppp)(2) (4), the first metalated hexavalent tellurium compound, which is formed by reaction of 2 with KF in the presence of MeOH.     

Sensitive and selective detection of silver(I) ion in aqueous solution using carbon nanoparticles as a cheap, effective fluorescent sensing platform

In this Letter, we demonstrate the first use of carbon nanoparticles (CNPs) obtained from carbon soot by lighting a candle as a cheap, effective fluorescent sensing platform for Ag(+) detection with a detection limit as low as 500 pM and high selectivity. We further demonstrate its practical application to detect Ag(+) in a real sample.     

Efficacious selective separation of U(VI) over Mo(VI) using novel 2,9-diamide-1,10-phenanthroline ligands: Liquid-liquid extraction and coordination chemistry

Uranium and molybdenum are important strategic elements. The production of ⁹⁹Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum. In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(VI) over Mo(VI). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(VI) over Mo(VI) gradually increased. The SF_U/Mo were around 10,000 at 4 mol/L HNO₃. Three stripping agents were tested with the stripping efficiency of Na₂CO₃ (5%) > H₂O > HNO₃ (0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(VI) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry, ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.     

The activation of small molecules by palladium(II) complexes: isolation of a novel formally palladium(I) complex

Bis(solvento)palladium(II) complexes are shown to have an unusually high ability to activate organic substrates. Thus [Pd(dpe)(Me₂CO)₂](ClO₄)₂, dpe = Ph₂PCH₂CH₂PPh₂, catalyses the hydrogenation of olefins at 30 °C under 1 atm pressure of hydrogen. Ketonic groups are not reduced. When the alcoholysis of silanes is catalysed by [Pd(dpe)(ROH)₂](ClO₄)₂, R = H, Me or Et. a remarkable brick-red palladium(I) complex [Pd₂(dpe)₂] (ClO₄)₂ is obtained. The potential of this complex as a catalyst for other reactions is emphasised.     

A novel retro-reaction strategy toward designing a selective fluorescence Cu(II) chemodosimeter

A novel C9 acridane-adduct, featuring ketobenzimidazole chelate, functions as a highly selective fluorescent chemodosimeter for Cu²⁺, while other metal ions pose little interferences, if any. The signaling strategy operates via the Cu²⁺-mediated retro-reaction, generating a strongly fluorescent acridinium ion at the expense of the weakly emitting probe.     

Diketene-based neat four-component synthesis of the dihydropyrimidinones and dihydropyridine backbones using silica sulfuric acid(SSA)

Heterocyclic skeleton building blocks to afford dihydropyrimidinones and dihydropyridines based on neat adducts of diketene,alcohols and aldehydes via silica sulfuric acid(SSA) catalyzed ring opening of diketene in four-component Biginelli-type and Hantzsch-type reactions are presented.     

Probing trace Pb(2+) using electrodeposited N,N'-(o-phenylene)-bis-benzenesulfonamide polymer as a novel selective ion capturing film

A novel film modified electrode for the determination of trace lead was developed in this work. The modified electrode was prepared by the electropolymerization of N,N′-(o-phenylene)-bis-benzenesulfonamide (PBSA) as the ion capturing reagent to create the functional film. The modified electrode shows a high selectivity towards Pb²⁺ over interfering cations, e.g. Cu²⁺, Cd²⁺, Co²⁺, Ni²⁺, Zn²⁺, Cr²⁺, and the calibration curve was linear in the concentration range of 2.0 × 10⁻⁹ to 1.0 × 10⁻⁷ M with correlation coefficient of 0.999. For 20 min accumulation, detection limit of 1.0 × 10⁻⁹ M was obtained at the signal to noise ratio of 3. Analytical availability of the modified electrode was demonstrated by the application for samples from pond water.     

p-Dimethylaminobenzaldehyde thiosemicarbazone: a simple novel selective and sensitive fluorescent sensor for mercury(II) in aqueous solution

A novel and simple fluorophore, p-dimethylaminobenzaldehyde thiosemicarbazone (DMABTS), was prepared in order to find available fluorescent chemosensor for mercuric ion in aquesous solution. DMABTS emitted fluorescence at 448 nm in aqueous solution and its fluorescence intensity was completely quenched upon interaction with Hg²⁺ ions, which should be attributed to the 1:1 complex formation between DMABTS and Hg²⁺. The binding constant of the complex was determined as 7.48 × 10⁶ mol l⁻¹. The linear range of quantitative detection of 0 to 5.77 × 10⁻⁶ mol l⁻¹ and the detection limit of 7.7 × 10⁻⁷ mol l⁻¹ for Hg²⁺ in the 6.3 × 10⁻⁶ mol l⁻¹ DMABTS aqueous solution were obtained from a calibration curve. The coexistence of several transition metal ions and anions did interfere the fluorometric titration of Hg²⁺ ion by less than 4% in the emission change.     

Development of ultra-high sensitive and selective electrochemiluminescent sensor for copper(II) ions: a novel strategy for modification of gold electrode using click chemistry

A promising and highly sensitive electrochemiluminescence (ECL) sensor for the detection of Cu(2+) based on Cu(+)-catalyzed click reaction is described in this paper. Firstly, 1-azidoundecan-11-thiol was assembled on the Au electrode surface via a simple thiol-Au reaction, then the propargyl-functionalized Ru(bpy)(3)(2+)-doped SiO(2) nanoparticles (Ru-SNPs) ECL probe was covalently coupled on the electrode surfaces via click chemistry. Cu(+), the catalyst for click chemistry, is derived from the electrolytic reduction of Cu(2+)via the Bulk Electrolysis with coulometry (BE) technique and without any reductants. It is found that the ECL intensity detected from the electrode surface has a linear relationship with the logarithm of Cu(2+) concentration in the range of 1.0 × 10(-15) to 1.0 × 10(-11) M with a detection limit of 1.0 × 10(-16) M. Also, the method is highly specific even in the presence of high concentrations of other metal cations. It has been applied to detect trace Cu(2+) in complex samples (hepatoma cell) without sample treatment.     

Manganese (II) selective PVC based membrane sensor using a Schiff base

N,N′,N″,N′′′-1,5,8,12-tetraazadodecane-bis(salicylaldiminato)(H₂L) has been used as ionophore for preparing Mn²⁺ selective sensor. Membranes of different composition with regard to ratio of H₂L:PVC:NPOE:NaTPB have been prepared and investigated. The best performance was obtained with the membrane of composition 10:150:150:10 (H₂L:PVC:NPOE:NaTPB) (w/w; mg). This membrane generated linear potential response in the concentration range of 5.0 × 10⁻⁶ to 1.0 × 10⁻¹ M with a Nernstian slope of 30.0 mV/decade of activity and fast response time (10 s). Hydrogen ion does not effect to the performance of sensor in the pH range 3.0-6.5. The sensor was found to be sufficient selective for Mn²⁺ over a number of alkali, alkaline and heavy metal ions and could therefore be used for the determination of manganese in various samples by direct potentiometry.     

Analyzing mechanisms in Co(i) redox catalysis using a pattern recognition platform

Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis. Despite the benefits brought by redox catalysis, establishing the precise nature of substrate activation remains challenging. Herein, we determine that a Co(i) complex bearing two N,N,N-tridentate ligands acts as a competent redox catalyst for the reduction of benzyl bromide substrates. Kinetic studies combining electroanalytical techniques with multivariable linear-regression analysis were conducted, disclosing an outer-sphere electron-transfer mechanism, which occurs in concert with C–Br bond cleavage. Furthermore, we apply a pattern recognition platform to distinguish between mechanisms in the activation of benzyl bromides, found to be dependent on the ligation state of the cobalt(i) center and ligand used.

Through kinetic studies combining electroanalytical techniques with multivariable linear-regression (MLR) analysis, a pattern recognition platform is established to determine the electron-transfer mechanism (inner-sphere or outer-sphere) of an electrochemical reduction of benzyl bromides, mediated by different cobalt complexes.