Fe-selective fluorescent probe based on rhodamine B and its application in bioimaging

A Rhodamine-based fluorescent and colorimetric chemosensor for Fe³⁺ ion, acetyl rhodamine-hydroxamate (ARH), was designed and synthesized. Upon mixed with Fe³⁺ in CH₃CN-H₂O (1:1, v/v), the spirolactam of ARH was opened, which resulted in the dramatic enhancement of both fluorescence and absorbance intensity as well as the color change of the solution. Background metal ions showed small or no interference with the detection of Fe³⁺. The Job's plot indicated the formation of 1:1 complex between ARH and Fe³⁺. Confocal laser scanning microscopy experiments showed that ARH could be used to detect Fe³⁺ in living cells.     

A fluorescent chemosensor for cysteine based on naphthalimide derivative in aqueous solution

Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize cysteine (Cys) in aqueous solution. The fluorescence enhancement of 1 was attributed to the cyclization reaction of 1 with Cys by 1:1 binding stoichiometry, which has been utilized as the basis of fabrication of the Cys-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Cys indicated that the methods can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Cys-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Cys with a linear range covering from 3.9 × 10⁻⁸ to 1.4 × 10⁻⁵ M and a detection limit of 7.8 × 10⁻⁹ M. And the chemosensor shows excellent selectivity for Cys over other amino acids. Moreover, the response of the chemosensor toward Cys is fast (response time less than 3 min). In addition, the chemosensor has been used for determination of Cys in serum samples with satisfactory results.     

A highly sensitive and selective colorimetric and off-on fluorescent chemosensor for Cu based on rhodamine B derivative

A new rhodamine B derivative colorimetric and fluorescent sensor (1) was synthesized by condensation reaction of rhodamine B hydrazide and 2,4-dihydroxybenzaldehyde, which showed reversible and highly selective and sensitive recognition toward Cu²⁺ over other examined metal ions. Upon addition of Cu²⁺, sensor 1 exhibits remarkably enhanced absorbance intensity and color change from colorless to pink in DMSO and MeCN aqueous buffer solution or pure MeCN, and shows significant off-on fluorescence accompanied by color changes from colorless to orange in MeCN. The sensor 1 was also successfully applied to the determination of Cu²⁺ in water samples.     

Imine-functionalized, turn-on fluorophore for DCP

A monopyrene-imine derivative 1 is a highly selective and sensitive “turn-on” fluorogenic probe for diethyl chlorophosphate (DCP), a stimulant for organophosphorus nerve agents. Upon addition of DCP to a solution of 1, a phosphoramidate was formed which exhibited an enhanced fluorescence emission at 425 nm. When exposed to DCP in the vapor phase, 1 impregnated on silica gel showed a sky-blue fluorescence.     

Per-6-ammonium-β-cyclodextrin/p-nitrophenol complex as a colorimetric sensor for phosphate and pyrophosphate anions in water

Using per-6-ammonium-β-cyclodextrin (per-6-NH₃⁺-β-CD) as an anion binding site and p-nitrophenol as a spectroscopic probe, a colorimetric sensor is developed for phosphate and pyrophosphate anions in water. Per-6-NH₃⁺-β-CD forms a 1:2 inclusion complex with p-nitrophenol as characterized by NOESY and ESI-MS spectra and it undergoes a distinct color change from colorless to intense yellow upon exposure to phosphate or pyrophosphate anions over other anions including perchlorate, ATP²⁻, ADP²⁻ and AMP²⁻. The seven ammonium groups of 1, bind phosphate (characterized by ESI-MS) or pyrophosphate anions specifically by electrostatic interaction. This naked eye sensing is significant for very low concentration (5 × 10⁻⁵ M) of anion with 1:2 ratio of host and guest.     

Novel carbazole/anthracene hybrids for efficient blue organic light-emitting diodes

Two novel carbazole/anthracene hybrided molecules, namely 2-(anthracen-9-yl)-9-ethyl-9H-carbazole (AnCz) and 2,7-di(anthracen-9-yl)-9-ethyl-9H-carbazole (2AnCz), were designed and synthesized via palladium catalyzed coupling reaction. The anthracene was attached either at the 2-site (AnCz) or at both 2,7-sites (2AnCz) of the central carbazole core to tune the conjugation state and the optoelectronic properties of the resultant molecules. Both of them show good solubility in common organic solvents. They also possess relatively high HOMO levels (−5.39 eV, −5.40 eV) that would facilitate efficient hole injection and be favorable for high power efficiencies when used in organic light-emitting devices (OLEDs). AnCz and 2AnCz were used as non-doped emitter to fabricate OLEDs by vacuum evaporation. Good performance was achieved with maximum luminance efficiency of 2.61 cd A⁻¹ and CIE coordinates of (0.15, 0.12) for AnCz, and 9.52 cd A⁻¹ and (0.22, 0.37) for 2AnCz.     

Novel pyrazoline-based selective fluorescent sensor for Zn in aqueous media

This work describes the preparation of a novel pyrazoline compound and the properties of its UV-vis absorption and fluorescence emission. Moreover, this compound can be used to determine Zn²⁺ ion with high selectivity and a low detection limit in the HEPES (20 mM HEPES, pH = 7.2, 50% (v/v) CH₃CN) buffer solution. This sensor forms a 1:1 complex with Zn²⁺ and shows a fluorescent enhancement by chelation enhanced fluorescence effect with good tolerance of other metal ions. In addition, this sensor is very sensitive with fluorometric detection limit of 0.12 μM.     

Preparation of Cu2O nano-colloid and its application as selective colorimetric sensor for Ag ion

Current work reports a method of preparation of stable yellow copper (I) oxide, nano-colloid by a solution route using Cu (II) salt solution and sodium borohydride. The reduction process was carried out in a controlled manner in air at around 50 °C in the presence of alginate matrix. The nanophase was characterized by techniques such as electronic spectroscopy, infrared spectroscopy, powder X-ray diffraction and transmission electron microscopy. Sensor property of the colloid for the detection of metal ions such as Ag⁺, Na⁺, K⁺, Ca²⁺, Pb²⁺, Cd²⁺, Zn²⁺, Hg²⁺, Mg²⁺ and As⁵⁺ has been studied at room temperature. A distinct color change from yellow to dark brown was noticed in the case of Ag⁺ ion. This is associated with a shift in ‘λ_max’ value from 448 nm to 478 nm. Whereas, no such significant visible color change was noticed on the addition of solutions containing other metal ions. Thus, in the present study Cu₂O nano-colloid was demonstrated as a highly specific and selective liquid colorimetric sensor for Ag⁺ ion.     

Efficient bluish-green phosphorescent iridium complex for both solution-processed and vacuum-deposited organic light-emitting diodes

Iridium(III)bis(4,6-(difluorophenyl)pyridinato-N,C^2′)picolinate (Firpic) is one typical bluish-green phosphor widely used in phosphorescent organic light-emitting diodes (PhOLEDs). In order to optimize its electroluminescent performance, 3,6-(di-tert-butyl)carbazolyl was introduced into the pyridine ring of the 2,4-difluorophenyl-pyridine ligand via a non-conjugated CH₂ linkage. The generated 3,6-di-tert-butyl-9-((6-(2,4-difluorophenyl)pridine-3-yl)methyl)-9H-carbazole (Cz-CH₂-dfppy) was used as cyclometalating ligand to prepare iridium complex 1, (Cz-CH₂-dfppy)₂Ir(pic). In comparison with the case to attach carbazole directly on pyridine, this non-conjugated CH₂ linking strategy avoids the unwanted bathochromic shift of the phosphorescence and improves the solubility of the iridium complex. (Cz-CH₂-dfppy)₂Ir(pic) (1) was used as doped emitter to fabricate OLEDs by both spin-coating and vacuum evaporation methods. Efficient bluish-green electrophosphorescence was obtained with maximum luminance efficiency of 22 cd/A (14 lm/W, 8.7%) and 26 cd/A (12 lm/W, 9.5%) for the solution-processed and vacuum-deposited devices, respectively, which far exceed those of the parent Firpic based device. The improved performance for (Cz-CH₂-dfppy)₂Ir(pic) was interpreted in terms of improved charge balance brought by the presence of the carbazole groups in the ligands.     

A simple band ratio technique to quantify the colored dissolved and detrital organic material from ocean color remotely sensed data

Spectral reflectances of the ocean, R, as derived from ocean color remote sensing data at four wavelengths (412, 443, 490, and 555 nm), can be used to form two ratios of spectral reflectance, namely R(412)/R(443), and R(490)/R(555), thereafter denoted R₄₄₃⁴¹² and R₅₅₅⁴⁹⁰. The former is mainly sensitive to the colored dissolved organic material (CDOM), albeit influenced by the algal content as depicted by the chlorophyll concentration, ([Chl]); in contrast, the latter is essentially depending on [Chl], although it is also influenced by CDOM. Therefore the signatures of CDOM and [Chl] which are not truly separable, can nevertheless be identified by considering simultaneously the two ratios. The concomitant variations in these ratios can be established via a bio-optical model developed for Case 1 waters. This model implicitly includes a “mean” relationship between CDOM and [Chl], and thus produces a unique curve relating R₄₄₃⁴¹² to R₅₅₅⁴⁹⁰. Deviations with respect to this mean relationship can be introduced through a factor Φ, with Φ > 1 (excess) or < 1 (deficit), applied to the CDOM-[Chl] ratio. A family of R₄₄₃⁴¹²-R₅₅₅⁴⁹⁰ curves is thus generated, in correspondence with the discrete values given to Φ; this “grid” (or numerically, a 2-D lookup table) allows the Φ-[Chl] couple to be unambiguously derived for any R₄₄₃⁴¹²-R₅₅₅⁴⁹⁰ couple. By applying this straightforward algorithm to actual reflectance ratios derived from ocean color imagery, the relative anomalies in CDOM with respect to its standard (Chl-related) values can be efficiently assessed. Within the global ocean (discarding the coastal zones), the Φ factor is widely varying, between at least ? and 3, and is roughly log-normally distributed around ~ 1 (no anomaly). The spatial distributions of the Φ factor in the whole ocean are strongly featured according to latitude, season, and hydrographic regimes, and these features are regularly reproducible, from year to year (2002-2007). This simple method is also validated against available in situ data, and its results compare favorably, for instance, to those of the GSM (Garver-Siegel-Maritorena) inversion method, in terms of retrieved CDOM concentrations and distribution patterns.     

Enhanced chemosensing of ammonia based on the novel molecular semiconductor-doped insulator (MSDI) heterojunctions

A series of new molecular semiconductor-doped insulator (MSDI) heterojunctions as conductimetric transducers to NH₃ sensing were fabricated based on a novel semiconducting molecular material, an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu₂[Pc(15C5)₄]₂[Pc(OC₁₀H₂₁)₈], quasi-Langmuir-Shäfer (QLS) film, as a top-layer, and vacuum-deposited and cast film of CuPc as well as copper tetra-tert-butyl phthalocyanine (CuTTBPc) QLS film as a sub-layer, named as MSDIs 1, 2 and 3, respectively. MSDIs 1-3 and respective sub-layers prepared from three different methods were characterized by X-ray diffraction, electronic absorption spectra and current-voltage (I-V) measurements. Depending on the sub-layer film-forming method used, α-phase CuPc film structure, β-phase CuPc crystallites and H-type aggregates of CuTTBPc have been obtained, respectively. An increasing sensitivity to NH₃ at varied concentrations in the range of 15-800 ppm, follows the order MSDI 2 < MSDI 3 < MSDI 1, revealing the effect of sub-layer film structures on sensing performance of the MSDIs. In particular, the time-dependent current plot of the MSDI 1, with α-phase CuPc film as a sub-layer, clearly shows an excellent separation of the different ammonia concentration levels and nearly complete reversibility and reproducibility even at room temperature, which is unique among the phthalocyanine-based ammonia sensors thus far reported in the literature. This provides a general method to improve sensor response of organic heterojunctions by controlling and tuning the film structure of sub-layer with appropriate fabrication techniques. On the other hand, the enhanced sensitivity, stability and reproducible response of the MSDI 1 heterostructure in comparison with the respective single-layer films have also been obtained. A judicious combination of materials and molecular architectures has led to enhanced sensing properties of the MSDI 1, in which control at the molecular level can be achieved.     

Salicylaldehyde based colorimetric and “turn on” fluorescent sensors for fluoride anion sensing employing hydrogen bonding

Two salicylaldehyde based colorimetric and fluorescent chemosensors 1 and 2 were developed. Both receptors 1 and 2 showed unique selectivity for the fluoride anions over other anions in DMSO solution. [TBA] OH and ¹H NMR titration experiments revealed that the F⁻-induced colorimetric and “turn on” fluorescence response were driven by hydrogen bonding interaction between the OH protons and F⁻.     

Interaction studies of human prion protein (HuPrP109–111: methionine-lysine-histidine) tripeptide model with transition metal cations

In the present study, the coordination bonds between the Methionine-Lysine-Histidine (Ac-MKH-NHMe) tripeptide model associated with the fifth metal binding site, which triggers the β-sheet formation of human prion protein and the divalent metal cations such as Mn²⁺, Cu²⁺ and Zn²⁺ were studied using B3LYP and M052X levels of theory with LANL2DZ basis set. For each transition divalent metal cation, three different coordination modes (4N, 3NO, and 2NSO) were analyzed. The present result reveals that overall structural parameters of MKH model tripeptide are altered due to the interaction of divalent metal cations. Among these three coordination modes, the 4N-M²⁺ and 4N2O-Mn²⁺ complexes are found to have the larger interaction energy, MIA and deformation energies. The triply deprotonated coordination mode of the Ac-MKH-NHMe tripeptide transfers more amount of charge to the divalent metal cations than the dually and singly deprotonated complexes. Furthermore, the atoms in molecules (AIM) topological analysis confirm that, the interaction between the metal cations Mn²⁺, Cu²⁺ and Zn²⁺ and Ac-MKH-NHMe tripeptide are electrostatic dominant and the coordination modes with triply deprotonation states possess larger electron density at their BCP corresponding to their coordination bonds. The electrostatic potential difference maps of the most stable 4N-M²⁺ (M²⁺ = Cu²⁺ and Zn²⁺) and 4N2O-Mn²⁺ reveals that, as the ionic radii of the metal ion increases, the delocalization charges localized on the metal cations are found to be decreased. The Infra-red stretching frequencies of NH, CH, and CH₂ groups of each coordination complexes are observed with shift in their stretching frequencies. From these observations we conclude that, the transition divalent metal cations binding in 4N coordination mode will induce more conformational changes of the Prion protein.     

Connected sum of digital closed surfaces

During the past 20 years the research of digital surfaces has proceeded to find their properties in the digital space Zⁿ, such as a topological number, a simple k-point, the 3D-Jordan theorem, a k-separating set, a boundary detecting algorithm and so on. Actually, unlike surfaces in a continuous space, the features of digital surfaces have different characteristics. The aim of this paper is to introduce the notion of a digital closed k-surface in Zⁿ, n ? 3, with the general k-adjacency relations as a generalization of Malgouyres’ and Morgenthaler’s k-surfaces in Z³, to establish some minimal simple closed k-surfaces in Z³ and to find their digital topological properties in relation with the k-fundamental group and k-contractibility. Moreover, a connected sum of two digital closed surfaces is introduced and its digital topological properties are investigated.     

Potentiometric solid-state sensor for DO measurement in water using sub-micron Cu0.4Ru3.4O7 + RuO2 sensing electrode

The dissolved oxygen (DO) sensing electrode (SE) concept utilizing sub-micron-sized ruthenium oxide (RuO₂), doped with other nanostructured oxides, has been extended to investigate the possibility of employing copper (II) oxide (Cu₂O) as a dopant in order to improve sensor's characteristics and meet long term antifouling needs for SEs. In this work, a thin-film SE made of RuO₂ was constructed on the alumina sensor substrate, and a range of dopants and their concentrations was added to it in order to optimize SE properties. The Cu₂O-doped RuO₂ SE had shown a linear response to DO between 0.5 and 8.0 ppm at various temperatures, with two sensitivity maxima of 47.4 and 46.0 mV per decade for Cu₂O concentrations of 10 and 20 mol%, respectively. The maximum sensitivity for Cu_0.4Ru_3.4O₇ + RuO₂-SE was obtained at a dopant concentration of 10%. Selectivity measurements revealed that the presence of Ca²⁺, Mg²⁺, Li⁺, Na⁺, NO³⁻, PO₄³⁻, SO₄²⁻, F⁻, K⁺ and Cl⁻ in the solution had no significant effect on the sensor's emf. The sensor allows overcoming the problem of an insufficient selectivity of semiconductor-based water sensors. It was also found that the doping of RuO₂-SE by Cu₂O allowed it to function at full capacity in a natural outdoor water body with no obvious effects of biofouling.     

A dual functional near infrared fluorescent probe based on the bodipy fluorophores for selective detection of copper and aluminum ions

A new near infrared (NIR) fluorescent 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye with dual functionality was synthesized and characterized. The compound 1 responds to copper ion in NIR region with high selectivity through a photo-induced electron transfer process established between the substituted benzene group in the meso position and the BODIPY core when Cu²⁺ binds with the four oxygen atoms in the structure, and results in the quenching of the fluorescence. The response range to copper ions was from 10 to 50 μM, and other metal ions including Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Pb²⁺, Fe³⁺, Ag⁺, Hg²⁺, Co²⁺, Zn²⁺, Mn²⁺, Cd²⁺, Ni²⁺ and Al³⁺ had no interference. When excited at 520 nm, a new emission peak at 568 nm of compound 1 was used to detect Al³⁺ selectively from 30 μM to 110 μM without any interference from other metal ions including copper ions.     

New fluorescent probes for mercury(II) with simple structure

Based on the protection reaction between ethanethiol and aldehyde, a novel fluorescent probe (2) for Hg²⁺ ions, with the simplest structure reported so far, was designed, which displayed high sensitivity and selectivity towards Hg²⁺ and Ag⁺ over other metal ions with detectable fluorescent signals, due to distinct deprotection reaction of dithioacetal. Compound 2 was further utilized to construct the chemical reaction-based conjugated polymer probes (P2 and P4) for Hg²⁺ ions. More importantly, the effect of the molecular weight of conjugated polymers on the sensitivity of the probes towards Hg²⁺ ions was carefully studied.     

Electrochemical performances of B doped and undoped diamond-like carbon (DLC) films deposited by femtosecond pulsed laser ablation for heavy metal detection using square wave anodic stripping voltammetric (SWASV) technique

Pure diamond-like carbon (DLC) thin films and boron-doped DLC thin films have been deposited on silicon substrates using femtosecond pulsed laser. The amorphous carbon materials (DLC), have been deposited at room temperature by ablating graphite targets with an amplified Ti:sapphire laser of 800 nm wavelength and a pulse duration of 150 fs in high vacuum conditions. Doping with boron has been performed by ablating alternatively graphite and boron targets.In this study, the DLC films were used as working electrodes for the electrochemical detection of trace heavy metals namely, Cd²⁺, Pb²⁺, Ni²⁺ and Hg²⁺, by using square wave anodic stripping voltammetry (SWASV) technique. Four metals were detected at −1.3 V deposition potential, and 90 s deposition time. The DLC films have been characterized by multiwavelength Raman spectrometry and high resolution scanning electron microscopy. The effect of the boron doping on the electrochemical behavior has been shown. The a-C:B 8%/Si₃N₄ electrode gives the more sensitive detection. The four metals are detected simultaneously with a detection limit of 1 μg/L or 2 μg/L and a dynamic range from 1 or 2 to 25 μg/L for every metal, as presented in third table of this article. The different sensitivities obtained are 6.2, 20.0, 1.2 and 6.6 μA/ppb or μA μg⁻¹ L for Cd²⁺, Pb²⁺, Ni²⁺ and Hg²⁺, respectively.     

A new acridine derivative as a highly selective ‘off-on’ fluorescence chemosensor for Cd in aqueous media

A new acridine fluoroionophore containing two diethanolamine ligands, 4,5-bis(N,N-di (2-hydroxyethyl)iminomethyl)acridine (BHIA), was designed and synthesized based on the fluorophore-spacer-receptor format. And its fluorescent sensing behavior towards metal ions was investigated in buffered aqueous media. The presence of Cd²⁺ induces the formation of a 1:1 ligand/metal complex at neutral pH, which exhibits enhanced emission at 454 nm. The fluorescence intensity is linear with the Cd²⁺ concentration in the range of 1.0 × 10⁻⁶ to 3.0 × 10⁻⁵ M (R = 0.9967). Experimental results show a low interference response towards other metal ions. The selective switch-on fluorescence response of BHIA to Cd²⁺ makes it suitable for sensing of Cd²⁺ in aqueous solution. The detection limit is 1.3 × 10⁻⁷ M. Moreover, the results indicated that BHIA was a reversible chemosensor for Cd²⁺, which makes it attractive for sensing applications.     

A Hg fluorescent chemosensor without interference from anions and Hg-imaging in living cells

A fluorescent chemosensor, B2, for Hg²⁺ containing a BODIPY fluorophore and carboxyl-thiol metal-bonding moieties was described. B2 exhibits selective fluorescence enhancement (123-fold) toward Hg²⁺ over other metal ions. Especially, the fluorescence enhancement was unaffected by anions existing in environment and organism. B2 shows high sensitivity to Hg²⁺ in a concentration of ppb range with detection limit of 77 nM. B2-ester, the membrane-permeable ethyl ester, is able to be hydrolyzed to B2 in vivo, and successfully applied to image intracellular Hg²⁺ in living cells.