An ESIPT-Based Fluorescent Probe for Wash-Free Cell Membrane Imaging.

The cell membrane tracking is important for studying the membrane function and diagnosing membrane-related diseases, so the development of fluorescent molecule specifically lighting up cell membrane is highly desirable. In this work, we designed and readily prepared a fluorescent dye (BOHI) that can target cell membrane. The pH-dependent emission spectra reveal that BOHI shows fluorescence based on the excited-state intramolecular proton transfer (ESIPT) under acidic and neutral conditions, while the blue-shifted emission from the phenolate anion of BOHI was observed when pH ≥ 9. Among various solvents, the weakest fluorescence emission was observed in H2O, which is favorable to wash-free imaging. The fluorescence intensity of BOHI is greatly affected by surfactants. The anionic surfactant can induce intense green fluorescence, while very weak fluorescence was observed in the solution of cationic surfactant. Hela cells images show that BOHI can specifically targets and lights up cell membrane.

3-Aroylbenzocoumarin-Based Luminogens: Bright Solid-State Emission, AIE Properties and Cell Imaging Application.

A series of 3-aroylbenzocoumarin-based luminogens have been synthesized for investigating their aggregation-induced emission (AIE) and solid-state fluorescence. The single crystal X-ray diffraction analysis of one of them showed that the molecules are arranged in the form of π-dimers which may lead to excimer emission. The large Stokes shifts and the broad-band emission of these 3-aroylbenzocoumarins in solid/aggregation state demonstrated the probable formation of excimers. The shapes of benzocoumarin units have a great effect on the AIE behaviors. The linear benzocoumarin derivatives show larger Stokes shifts, while the bent-benzocoumarin derivatives exhibit better AIE performances. All of them show aggregation-enhanced excimer emission which is supported by the large Stokes shifts. The electronic effect of 3-aroyl groups also has a certain effect on their fluorescence properties. The polymorphism phenomenon was observed for one of the benzoyl-containing derivatives. Additionally, two of the derivatives containing methoxy group were successfully used for cell imaging.

Excimer emission from polycyclic arenes bearing triphenylmethyl group: Solid-state fluorescence, mechanofluorochromism, aggregation-induced emission and cell imaging application.

The excimer emission based on discrete π-stacked dimers of polycyclic π-systems has generated significant interest in the structure-luminescence relationship of excimers owing to their ultra-large Stokes shift. Herein, a series of excimer emissive luminogens were obtained by conjugating different polycyclic aromatic aldehydes (anthraldehyde, pyrenealdehyde and perylenealdehyde) with triphenylmethylamine. In crystalline states, all the molecules were arranged in the form of π-stacked arene dimers which were spatially isolated from each other by the bulky triphenylmethyl groups, and thus emitted bright excimer emission. The anthracene and pyrene derivatives showed fluorescence enhancement responses to grinding and the enhanced fluorescence could recover to the original state upon heating. The aggregation-induced emission (AIE) properties of them were dependent on the shapes and sizes of the polycyclic aromatic groups. The pyrene derivative showed the most excellent excimer-based AIE behavior among them. All of them were more apt to exhibit the excimer emission when formed nanoparticles with pluronic F-127 than that without pluronic F-127. Furthermore, PETP was utilized for bioimaging of living Hela cells and the high-resolution image was observed.

Substituent Effects on Fluorescence Properties of AIEgens Based on Coumarin-3-formylhydrazone and their Application in Cell Imaging.

AIE-active compounds have lately attracted considerable attention owing to their versatile applications, especially in OLED and bioimaging. Herein, a series of coumarin-3-formylhydrazone derivatives (CFH-1, 2, 3 and 4) were developed for investigating their AIE and solid-state luminescence behaviors. All the obtained compounds emit varying degrees of solid-state fluorescence. CFH-1 and 2 show the typical AIE characteristics, while CFH-3 and 4 exhibit stronger solution fluorescence than their aggregation-induced emission. The single crystal X-ray diffraction analysis of CFH-1 and CFH-3 showed that both of them adopt planar conformation and the CH···O hydrogen bonding plays a crucial role in their crystal packing. Meanwhile, there is a notable difference between them. Successive π-π stacking interaction was observed in the crystal packing of CFH-1, while the crystals of CFH-3 contain dimeric π-π stacking interaction. Their distinct crystal packing interactions result in their different fluorescence properties. Moreover, both CFH-1 and CFH-2 displayed excellent bioimaging performances in living cells.

Adsorption of Pb (II) ions on variable charge oxidic calcined substrates with chemically modified surface.

Background: The paper describes lead ion adsorption on variable charge oxidic calcined substrates with chemically modified surfaces. Amphoteric oxides of iron, aluminum, titanium, and manganese, change their surface electric charge after acid or alkaline treatment, letting cationic or anionic adsorption reactions from aqueous solutions. This property allows using them as adsorbing substrate for heavy metals retention in water treatment systems. Methods: Substrate was prepared by extruding cylindrical strips from a saturate paste of the oxidic lithological material-OLM; dries it up and thermally treated by calcination. The study was performed by triplicated trial, on batch mode, using 2 grams samples of treated with NaOH 0.1N and non-treated substrate. Lead analysis was performed by AAS-GF. Freundlich and Langmuir models were used to fit results. Comparing differential behavior between treated and non-treated substrates showed the variable charge nature of the OLM. Results: Results show L-type isotherms for the adsorption of Pb(II) ions on the activated substrate, suggesting good affinity between Pb(II) ions and OLM's surface. Average value of adsorption capacity ( K) for activated substrate (1791.73±13.06), is around four times greater than the non-activated substrate (491.54±31.97), during the adsorption reaction, 0.35 and 0.26 mmolH + of proton are produced on the activated and non-activated substrate respectively using a 1 mM Pb(II) solution and 72.2 and 15.6 mmolH + using a 10 mM Pb(II) solution. This acidification agrees with the theoretic model of transitional metals chemisorption on amphoteric oxides, present in lithological material used for the preparation of adsorbent substrates, confirming the information given by the L-type isotherms. Conclusions: Results suggest that these variable charge oxidic adsorbent substrate show great potential as an alternative technique for water treatment at small and medium scale using granular filtration system. The easiness and low price make them suitable to apply in rural media where no treating water systems is available.

Wavelength-tunable AIEgens based on 6-methoxy-2-naphthaldehyde: AIE behavior and bioimaging performance.

AIE-active dyes have lately received considerable attention due to their versatile applications, especially in bioimaging and theranostics. Herein, 6-methoxy-2-naphthaldehyde was used to construct fluorophores through Knoevenagel condensation with various active methylene compounds. All the obtained compounds showed varying degrees of AIE characteristics. It was worth mentioning that the condensation product of 6-methoxy-2-naphthaldehyde and malononitrile (MOP-e) exhibited a large redshift and a large Stokes shift when forming aggregates. Furthermore, it showed an ultra-wide AIE band which enabled it to be utilized for dual-channel bioimaging. The single crystal X-ray diffraction analysis showed that two different molecular arrangement modes, the monomolecular stacking and the discrete π-π dimeric stacking, existed in the aggregates of MOP-e. The discrete dimeric stacking leads to excimer-induced enhanced emission, which results in its unique AIE behavior. Moreover, MOP-e displayed an excellent bioimaging performance in living cells in green channel and in red channel respectively.

An AIE-Active probe for detection and bioimaging of pH values based on lactone hydrolysis reaction.

Cellular pH homeostasis is essential for many physiological and pathological processes. pH monitoring is helpful for the diagnosis, treatment and prevention of disorders and diseases. Herein, we developed a ratiometric fluorescent pH probe (TCC) based on a coumarin derivative containing a highly active lactone ring. TCC exhibited a typical AIE effect and emitted blue fluorescence under weak acidic condition. When under weak basic condition, the active lactone moiety underwent a hydrolysis reaction to afford a water-soluble product, which gave red-shifted emission. The emission color change from blue through cyan and then to yellow within pH 6.5-9.0 which is approximate to the biological pH range. And the fluorescence color change along with pH value is reversible. Furthermore, TCC was successfully utilized in the detection of the intracellular pH change of live HeLa cells, which indicated that TCC had practical potential in biomedical research.

Substituent Effect on AIE mechanism of two coumarin derivatives: uncommon TICT fluorescence in aggregation state.

Two coumarin derivatives, 7-diethylamino-3-(4-nitrophenyl)coumarin (DNC) and 7-hydroxy-3-(4-nitrophenyl)coumarin (HNC), were synthesized via Knoevenagel condensation of salicylaldehyde derivatives with 4-nitrophenylacetonitrile and then cyclization reaction. Both of them were characterized by single-crystal X-ray diffraction. The molecules of DNC are stacked via π-π interaction, while the hydrogen bond interactions instead of π-π interaction were observed in the crystal packing of HNC. Both of DNC and HNC showed solvatochromic properties and aggregation-induced emission (AIE) activities, but the AIE characteristics of them were entirely different. HNC exhibited an AIE phenomenon as the result of the restriction of twisted intramolecular charge transfer (TICT), while DNC emitted peculiar dual fluorescence which was assigned to the emission based on the inhibition of TICT state formation and the emission from the TICT state respectively.

Benzothiazolylhydrazone-Based Turn-on Fluorescent Probe for Detecting Cu2+: S-donor as a Cu2+-induced Fluorescence Quenching Inhibitor.

The fluorescent turn-on detection of metal ions is highly desirable for public health and environmental security. Herein, we report a rationally designed fluorescent probe (1) for the detection of Cu2+ synthesized by integrating 2-hydrazinylbenzothiazole with 3-acetyl-7-hydroxycoumarin. The probe alone is non-fluorescent due to the isomerization of C=N in the excited state. The addition of Cu2+ can cause a delayed fluorescence enhancement. A comparative study of 1 and its analogues indicated that the turn-on fluorescence response was thanks to the sulfur atom coordinating to Cu2+. The response delay of 1 in sensing Cu2+ was ascribed to the gradual transition from N-coordination to S-coordination (N and S in thiazole moiety). The proposed new function of S-donor would provide a new approach for the turn-on fluorescence sensation of Cu2+.

A Dual-Target Fluorescent Probe with Response-Time Dependent Selectivity for Cd2+ and Cu2.

A novel fluorescent probe (NT) was developed by merging 2-hydrazinylbenzothiazole with 2-hydroxy-1-naphthaldehyde for the detection of Cd2+ and Cu2+. The probe alone is almost nonfluorescent due to the isomerization of C=N in the excited state. The addition of Cd2+ can cause an immediate strong green fluorescence owing to the suppression of C=N isomerization by Cd2+-coordination. Furthermore, NT gives a delayed turn-on fluorescence response to Cu2+ although it is a vigorous fluorescence quencher, which was thanks to the inhibition of the electron transfer between excited fluorophore and paramagnetic Cu2+ by sulfur donor. Based on fluorescence spectra and ESI-MS analysis, the binding modes between NT and Cd2+/Cu2+ were proposed.

A Dansyl-Rhodamine Based Fluorescent Probe for Detection of Hg2+ and Cu2.

A novel fluorescent probe based on dansyl-appended rhodamine B was developed. The probe can selectively recognize and sense Hg2+ and Cu2+ from other common metal ions by showing unique fluorescence and absorption characteristics. In MeCN/HEPES buffer solution, the probe gives a ratiometric fluorescent response to Hg2+, which was ascribed to the fluorescence resonance energy transfer from dansyl moiety to the ring-opened rhodamine B moiety, while the presence of Cu2+ causes fluorescence quenching. Beside the fluorescence change, the presence of Cu2+ and Hg2+ can induce intensive absorption at about 555 nm, which resulted in a color change from colorless to pink.

A Rhodamine-Based Fluorescent Chemosensor for the Detection of Pb2+, Hg2+ and Cd2.

A new rhodamine-based fluorescent chemosensor (1) has been designed and synthesized by linking rhodamine 6G hydrazide with N-methylisatin via an imine linkage. The receptor can selectively recognize and sense Pb2+, Hg2+ and Cd2+ by showing different fluorescence characteristics. In ethanol/HEPES buffer medium, the addition of Cd2+ caused a yellowish-green fluorescence, while the presence of Pb2+ or Hg2+ gave rise to an orange fluorescence. Additionally, the sensor shows an irreversible fluorescence response to Pb2+ and reversible fluorescence responses to Hg2+ and Cd2+.

The development of anticancer ruthenium(ii) complexes: from single molecule compounds to nanomaterials.

Cancer is rapidly becoming the top killer in the world. Most of the FDA approved anticancer drugs are organic molecules, while metallodrugs are very scarce. The advent of the first metal based therapeutic agent, cisplatin, launched a new era in the application of transition metal complexes for therapeutic design. Due to their unique and versatile biochemical properties, ruthenium-based compounds have emerged as promising anti-cancer agents that serve as alternatives to cisplatin and its derivertives. Ruthenium(iii) complexes have successfully been used in clinical research and their mechanisms of anticancer action have been reported in large volumes over the past few decades. Ruthenium(ii) complexes have also attracted significant attention as anticancer candidates; however, only a few of them have been reported comprehensively. In this review, we discuss the development of ruthenium(ii) complexes as anticancer candidates and biocatalysts, including arene ruthenium complexes, polypyridyl ruthenium complexes, and ruthenium nanomaterial complexes. This review focuses on the likely mechanisms of action of ruthenium(ii)-based anticancer drugs and the relationship between their chemical structures and biological properties. This review also highlights the catalytic activity and the photoinduced activation of ruthenium(ii) complexes, their targeted delivery, and their activity in nanomaterial systems.

Luminescence response of an osmium(II) complex to macromolecular polyanions for the detection of heparin and chondroitin sulfate in biomedical preparations.

Heparin, dextran sulfate (DS), chondroitin sulfate (CS), and carrageenan are found to enhance the luminescence intensity of an osmium(II) carbonyl complex with phenanthroline (phen) and 4-phenylpyridine (4-phpy) ligands in aqueous and ethanol solutions. The enhancing effect of the polyanions on the luminescence of the complex is heavily dependent on the sulfate content and other factors such as structure, solubility, and counter ions of the polyanion. The highly sulfated dextran and ι-carrageenan have the most profound effect, while the low charged κ-carrageenan and CS have the least response in aqueous solution. All polyanions exhibited enhanced luminescence intensity of the complex in ethanol solutions, and even the low charged CS and κ-carrageenan enhanced the luminescence more than 4 times. DS contamination of the sodium heparin at 5% can show a significant increase in luminescence response. The osmium complex is found to be highly successful in the fast and sensitive detection of heparin in commercial injectable samples with various backgrounds as well as the detection of CS in over the counter food supplement tablets.

Investigation of Luminescence Characteristics of Osmium(II) Complexes in the Presence of Heparin Polyanions.

The luminescence characteristics of six osmium carbonyl complexes with phenanthroline (phen) or bipyridine (bpy) and pyridine (py), 4-phenylpyridine (4-phpy), or triphenylphosphine (PPh3) complexes in the presence of polyanion heparin were studied in both ethanol and aqueous solutions. The influence of heparin on the luminescence of the complexes is heavily dependent on the type of ligands in the complexes and the solvent used. In the ethanol solutions, the heparin solution enhanced the luminescence of the five osmium complexes, with the strongest enhancement to the 4-phenylpyridine complexes; linear curves were obtained in the luminescence enhancement ratio (F/F 0) versus the heparin concentration range of 1-40 µ g/mL. In aqueous solutions, heparin quenching of the complexes was more significant; a linear quenching curve was obtained with [Os(phen)2CO(PPh3)](PF6)2 in the lower concentration range of 1-12 µ g/mL. The interaction of these complexes with heparin in the solutions is discussed. The complexes are shown to be successful in the fast and sensitive detection of heparin in commercial injectable samples.

rac-4-[4-Cyano-2-(hy-droxy-meth-yl)phen-yl]-4-(4-fluoro-phen-yl)-4-hy-droxy-N,N-dimethyl-butanaminium hemifumarate.

In the title salt, C(20)H(24)FN(2)O(2) (+)·0.5C(4)H(2)O(4) (2-), the fumarate anion is located on an inversion centre. In the cation, the two benzene rings are nearly perpendicular to each other, making a dihedral angle of 87.41 (10)°. The cation is linked to the anion by a bifurcated N-H⋯O hydrogen bond. Classical O-H⋯O and weak C-H⋯F hydrogen bonding is also present in the crystal structure. Three C atoms of the N,N-dimethyl-butanaminium moiety are disordered over two sites with refined site occupancies of 0.466 (14) and 0.534 (14).

2-(Biphenyl-4-yl-oxy)acetic acid.

In the title compound, C(14)H(12)O(3), the phenyl and benzene rings make a dihedral angle of 47.51 (4)°. In the crystal, mol-ecules are dimerized by double O-H⋯O hydrogen bonds, forming centrosymmetric R(2) (2)(8) ring motifs. The dimers are inter-linked by C-H⋯π inter-actions into zigzag layers.

3-[4-(2-Amino-2-oxoeth-yl)phen-oxy]-2-hy-droxy-N-isopropyl-propanaminium 1,1'-binaphthyl-2,2'-diyl phosphate.

In the title salt, C(14)H(23)N(2)O(3) (+)·C(20)H(12)O(4)P(-), the dihedral angle between the two naphthyl ring systems in the anion is 57.77 (6)°. In the crystal, an O-H⋯O hydrogen bond links the components. The ammonium group engages in N-H⋯O hydrogen bonds, generating a layer structure.

Crystal structure of a cyclomaltoheptaose-4-hydroxybiphenyl inclusion complex.

The crystal structure of the inclusion complex of cyclomaltoheptaose (beta-cyclodextrin) with 4-hydroxybiphenyl was determined by single-crystal X-ray diffraction at 150K. The complex contains two cyclomaltoheptaose molecules, two 4-hydroxybiphenyl molecules, one ethanol molecule and fifteen water molecules in the asymmetric unit, and could be formulated as [2(C(42)H(70)O(35)).2(C(12)H(10)O).(C(2)H(6)O).15(H(2)O)]. It crystallized in the triclinic space group P1 with unit cell constants a=15.257(3), b=15.564(3), c=15.592(2)A, alpha=104.485(15) degrees , beta=101.066(14) degrees , gamma=104.330(17) degrees , V=3,343.6(10)A(3). In the crystal lattice, two beta-cyclodextrins form a head-to-head dimer jointed through hydrogen bonds. Two 4-hydroxybiphenyls were included in the dimer cavity with their hydroxyl groups protruding from two primary hydroxyl sides of the cyclodextrin molecules. The guest 4-hydroxybiphenyl molecules linked into a chain via a combination of an O-Hcdots, three dots, centeredO hydrogen bond and face-to-face pi-pi stacking of the phenyl rings. The crystal structure supports the calculation results indicating that the 2:2 inclusion complex formed by beta-cyclodextrin and 4-hydroxybiphenyl is the energetically favored structure.

The crystal structure of the 1:1 inclusion complex of beta-cyclodextrin with benzamide.

The 1:1 inclusion complex of beta-cyclodextrin and benzamide was prepared and characterized by single crystal X-ray diffraction, PXRD, TGA, and IR. This complex crystallizes in the monoclinic P2(1) space group with unit cell constants a=15.4244(16), b=10.1574(11), c=20.557(2)A, beta=110.074(2) degrees , V=3025.1(6)A(3). The guest molecule projects into the beta-cyclodextrin cavity from the primary hydroxyl side. The amide group protrudes from the primary hydroxyl side and forms hydrogen bonds with the adjacent beta-cyclodextrin molecule. There are six crystallized water molecules, which play crucial roles in crystal packing.