A rhodamine-based fluorescent probe used to determine nitroxyl (HNO) in lysosomes.

The reactive nitrogen species (RNS) in lysosomes play a major role during the regulation of lysosomal microenvironment. Nitroxyl (HNO) belongs to active nitrogen species (RNS) and is becoming a potential diagnostic and therapeutic biomarker. However, the complex synthesis routes of HNO in biosystem always hinder the exact determination of HNO in living cells. Here, a rhodamine-based fluorescent probe used to determine nitroxyl (HNO) in lysosomes was constructed and synthesized. 2-(Diphenylphosphino)benzoate was utilized as the sensing unit for HNO and morpholine was chose as the targeting group for lysosome. Before the addition of HNO, the probe displayed a spirolactone structure and almost no fluorescence was found. After the addition of HNO, the probe existed as a conjugated xanthene form and an intense green fluorescence was observed. The fluorescent probe possessed fast response (3 min) and high selectivity for HNO. Furthermore, fluorescence intensity of the probe linearly related with the HNO concentration in the range of 6.0 × 10-8 to 6.0 × 10-5 mol L-1. The detection limit was found to be 1.87 × 10-8 mol L-1 for HNO. Moreover, the probe could selectively targeted lysosome with excellent biocompatibility and had been effectually utilized to recognize exogenous HNO in A549 cells.

Fluorogenic Rhodamine Probes with Pyrrole Substitution Enables STED and Lifetime Imaging of Lysosomes in Live Cells.

Fluorogenic dyes with high brightness, large turn-on ratios, excellent photostability, favorable specificity, low cytotoxicity, and high membrane permeability are essential for high-resolution fluorescence imaging in live cells. In this study, we endowed these desirable properties to a rhodamine derivative by simply replacing the N, N-diethyl group with a pyrrole substituent. The resulting dye, Rh-NH, exhibited doubled Stokes shifts (54 nm) and a red-shift of more than 50 nm in fluorescence spectra compared to Rhodamine B. Rh-NH preferentially exists in a non-emissive but highly permeable spirolactone form. Upon binding to lysosomes, the collective effects of low pH, low polarity, and high viscosity endow Rh-NH with significant fluorescence turn-on, making it a suitable candidate for wash-free, high-contrast lysosome tracking. Consequently, Rh-NH enabled us to successfully explore stimulated emission depletion (STED) super-resolution imaging of lysosome dynamics, as well as fluorescence lifetime imaging of lysosomes in live cells.

ß-Cyclodextrin-Encapsulated Rhodamine Derivatives Core-Shell Microspheres-Based Fluorescent Sensor for Au3+ and Template for Generating Microplates of Gold.

We have developed ß-cyclodextrin-encapsulated rhodamine derivative core-shell microspheres (ß-CD@RH) to improve their aqueous solubility and biocompatibility. The ß-CD@RH core-shell microspheres exhibited bright and stable fluorescence with Au3+ ion in aqueous media. The development of triangular and hexagonal gold microplates within an aqueous solution by a simple, one-step, and green chemistry strategy is followed and prepared. Fluorescent imaging of Au3+ in living cells is also successfully demonstrated.

An upconversion nanosensor with phenolic-like functionality for accurate identification of chlorpyrifos in grapes.

The inappropriate use of the organophosphorus pesticide chlorpyrifos (CPF) in agricultural production could be harmful to the environment and non-target organisms. Here, we prepared a nano-fluorescent probe with phenolic function based on covalently coupled rhodamine derivatives (RDP) of upconverted nano-particles (UCNPs) for trace detection of chlorpyrifos. Due to the fluorescence resonance energy transfer (FRET) effect in the system, the fluorescence of UCNPs is quenched by RDP. The phenolic-functional RDP is converted to the spironolactone form when it captures chlorpyrifos. This structural shift prevents the FRET effect in the system and allows the fluorescence of UCNPs to be restored. In addition, the 980 nm excitement conditions of UCNPs will also avoid interference from non-target fluorescent backgrounds. This work has obvious advantages in terms of selectivity and sensitivity, which can be widely applied to the rapid analysis of chlorpyrifos residues in food samples.

Scalable Production of Self-Toughening Plant Oil-Based Polyurethane Elastomers with Multistimuli-Responsive Functionalities.

Plant oils are becoming of high industrial importance due to the persisting challenges befalling with the utilization of fossil fuels. Thus, developing methodologies to produce multifunctional materials by taking advantage of the unique structure of plant oil is highly desired. In this study, castor oil served as a cross-linker and soft segments, by incorporating scalable rhodamine 6G derivatives, to systematically synthesize a series of smart polymers that possess self-toughening and multistimuli-responsive capabilities. The polyurethane elastomers showed 10 times and 60 times increases in tensile strength and toughness, respectively, in comparison with the unmodified polyurethane due to the existence of large amounts of hydrogen bonding, dynamic C-N spiro bonds, rigid benzene ring, and high cross-link densities. The novel polyurethane elastomers exhibited excellent reversible multichromic behaviors in response to light, pH, and mechanics. Notably, the resulting polyurethane elastomers exhibited ultrasensitive sustained photochromism with tunable white emission and rapid reversibility. This study provides a simple and effective strategy to utilize plant oil for multifunctional material preparation and paves the way to open access for application of plant oil-based products in a variety of industry applications, such as sensors, self-fitting tissue scaffolds, and switchable devices.

Sub-ppb mercury detection in real environmental samples with an improved rhodamine-based detection system.

A new procedure is described for the determination of Hg2+ ions in water samples. A Rhodamine based fluorescent sensor was synthesized and the experimental conditions were specifically optimized for application to environmental samples, which requires low detection limits and high selectivity in competitive experiments with realistic concentrations of other metal ions. Incorporation of a Rhodamine-6G fluorophore to a previously described sensor and optimization of the buffer system (detection with acetic acid at pH 5.25) enabled significant enhancement of the sensitivity (detection limit = 0.27 µg L-1) and selectivity. The optimized procedure using high-throughput microplates has been applied to tap and river waters with good results.

A novel rhodamine-based colorimetric and fluorometric probe for simultaneous detection of multi-metal ions.

Effective and simultaneous detection of multi-metal ions has been achieved by a colorimetric and fluorometric probe (REHBA) synthesized from rhodamine hydrazide and polyhydroxyl aromatic aldehyde. REHBA can serve as a colorimetric detector for Cu2+ and Co2+, and a fluorometric probe for Pb2+. The colorless solution of REHBA changes to pink for Cu2+/Co2+ and shows a remarkable fluorescence for Pb2+. The further differentiation of Cu2+ and Co2+ depends on whether the colorimetric response of REHBA is reversible upon addition of ethylene diamine tetraacetic acid. The response is reversible for Cu2+, while it is not for Co2+. The spirolactam ring-opening in REHBA and the formation of REHBA-metal complexes with binding stoichiometric ratio of 1:1 are responsible for the UV-visible and fluorescence behaviors. REHBA shows excellent selectivity, anti-interference and good sensitivity. The limit of detection of Cu2+, Co2+ and Pb2+ is 0.11 µM, 0.88 µM and 0.73 µM, respectively. In addition, REHBA has been applied to recognize Pb2+ in living cells by fluorescence image and Cu2+, Co2+ and Pb2+ in real water samples, indicating that REHBA is a potential candidate for multi-metal-ions detection.

A near-infrared rhodamine-based lysosomal pH probe and its application in lysosomal pH rise during heat shock.

Heat shock is a potentially fatal condition characterized by high body temperature (>40 °C), which may lead to physical discomfort and dysfunctions of organ systems. Acidic pH environment in lysosomes can activate enzymes, thus facilitating the degradation of proteins in cellular metabolism. Owing to the lack of a practical research tool, it remains difficult to exploit relationship between heat shock and lysosome. Herein, a NIR lysosomal pH chemosensor (NRLH) was developed. One typical lysosome-locating group, morpholine, was incorporated into NRLH. The fluorescence intensity showed pH-dependent characteristics and responded sensitively to pH fluctuations in the pH range of 3.0-5.5. NRLH with a pKa of 4.24 displayed rapid response and high selectivity for H+ among common species. We also demonstrated NRLH was capable of targeting lysosomes. Importantly, NRLH was applied in cellular imaging and the data revealed that lysosomal pH increased but never decreased during the heat shock. Therefore, NRLH may act as an effective molecular tool for exploring the mechanisms of heat-related pathology in bio-systems.

A Colorimetric and Fluorescent Indicator for Hg2+ Detection Based on Cinnamamide Group-Containing Rhodamine Derivative.

A colorimetric and fluorescent indicator based on cinnamamide group-containing rhodamine derivative was synthesized for the detection of Hg2+. The rhodamine B and cinnamamide were connected via ethylenediamine as a bridging molecule through a condensation reaction to obtain a colorimetric and fluorescent indicator for the detection of Hg2+ in H2O-EtOH (4:1, v/v). The indicator was excellent in the selectivity of Hg2+ and was almost unaffected by other common ions such as Na+, K+, Mg2+, Fe3+, Cu2+, Zn2+, Cr3+. The Hg2+-containing aqueous solution turned from colorless to red within 7 min after the addition of the indicator, and had an absorption peak at 564 nm in UV-vis, which implies a significant colorimetric phenomenon. Their characteristic peaks varied with the Hg2+ content, and they reached a linear relationship at low concentrations. The binding stoichiometry proved to be 1:1. The lowest detection limit was 4.1 × 10-7 mol/L, ranging from acidic to neutral.

Highly sensitive and selective determination of Hg(II) based on microfluidic chip with on-line fluorescent derivatization.

In this study, a convenient, sensitive, rapid and simple method was developed on microfluidic chip which was integrated with on-line complexing and laser-induced fluorescence detection. A rhodamine derivative (RD) was developed as a fluorescent chemosensor for Hg(II). It exhibited high selective recognition toward Hg(II) over other examined metal ions in water samples. Under the optimized conditions, the response was linearly proportional to the concentration of Hg(II) in the range of 0-70 µM with a detection limit of 0.031 µM. Satisfactory repeatability and reproducibility were achieved, with a relative standard deviation (RSD) of 6.62%. The established method was successfully applied for the determination of Hg(II) in environmental water samples (surface water, tap water, and waste water). Recoveries obtained for the determination of Hg(II) in spiking samples ranged from 85% to 103%.

A Rhodamine Derivative Based Chemosensor with High Selectivity and Quick Respond to Cr3+ in Aqueous Solution.

In this paper, a new kind of colorimetric chemsensor aiming at detecting Cr3+ has been synthesized, and it is based on the "Off-On" effect of a rhodamine derivative. Comparing with other metal irons (Na+, K+, Ni2+, Hg2+, Fe3+, Mn2+, Co2+, Cd2+, Cu2+, Pb2+, Zn2+, Mg2+, Ba2+, Ag+, Fe2+, Ce3+), the chemsensor has a quick and accurate response to Cr3+ in H2O-EtOH solution (4/1, v/v). There is an obvious change in color, from colorless to bright pink when Cr3+ is detected. According to the fitting curve based on Benesi-Hildebrand equation and working curve of absorption strength in UV-vis spectrum, the binding pattern of Cr3+ and the rhodamine derivative follows a 1:1 stoichiometry. The chemsensor shows great potential in monitoring Cr3+ in the aqueous medium with high efficiency, which is supposed to complete the recognition in the minimum as 5.2 × 10-7 mol/L within 5 min.

Two emissive-magnetic composite platforms for Hg(II) sensing and removal: The combination of magnetic core, silica molecular sieve and rhodamine chemosensors.

In this paper, a composite sensing platform for Hg(II) optical sensing and removal was designed and reported. A core-shell structure was adopted, using magnetic Fe3O4 nanoparticles as the core, silica molecular sieve MCM-41 as the shell, respectively. Two rhodamine derivatives were synthesized as chemosensor and covalently immobilized into MCM-41 tunnels. Corresponding composite samples were characterized with SEM/TEM images, XRD analysis, IR spectra, thermogravimetry and N2 adsorption/desorption analysis, which confirmed their core-shell structure. Their emission was increased by Hg(II), showing emission turn on effect. High selectivity, linear working curves and recyclability were obtained from these composite samples.

Hg(II) sensing platforms with improved photostability: The combination of rhodamine derived chemosensors and up-conversion nanocrystals.

This paper reported two nanocomposite sensing platforms for Hg(II) detection with improved photostability, using two rhodamine derivatives as chemosensors and up-conversion nanocrystals as excitation host, respectively. There existed a secondary energy transfer from this excitation host to these chemosensors, which was confirmed by spectral analysis, energy transfer radius calculation and emission decay lifetime comparison. In this case, chemosensor photostability was greatly improved. Further analysis suggested that these chemosensors recognized Hg(II) following a simple binding stoichiometry of 1:1. Hg(II) sensing performance of these sensing platforms was analyzed through their emission spectra upon various Hg(II) concentrations. Emission spectral response, Stern-Volmer equation, emission stability and sensing selectivity were discussed in detail. It was finally concluded that these chemosensors showed emission turn on effect towards Hg(II), with high photostability, good selectivity and linear response.

A Colorimetric and Fluorescent Sensor for Iron Recognition Based on Rhodamine Derivative.

A novel rhodamine based fluorescent sensor, L, was developed and investigated as a colorimetric and fluorescent sensor for Fe3+ in dimethyl sulfoxide. The compound L showed a good selectivity and sensitivity toward Fe3+ in the presence of large excess of other competitive ions. L can be used as a colorimetric and fluorescent sensor for Iron recognition in potential.

Recyclable Magnetic Mesoporous Nanocomposite with Improved Sensing Performance toward Nitrite.

A magnetic nanomaterial for nitrite ion detection was demonstrated in the present study. This nanomaterial was prepared by grafting a rhodamine 6G derivative (denoted as Rh 6G-OH) into the channels of core-shell magnetic mesoporous silica nanospheres. The nanocomposite (denoted as Fe3O4@Rh 6G) showed large surface area and improved fluorescent performance to accumulate and recognize NO2(-), and its superparamagnetic behavior played an important role in reusability. The fluorescent intensity decreased linearly along with the NO2(-) concentration in the range of 1-50 µM, and the detection limit was estimated to be 0.8 µM, which was much lower than the maximum limit of nitrite ion in drinking water (65 µM) recommended by World Health Organization. Importantly, Fe3O4@Rh 6G could be magnetically collected and effectively reutilized after six test cycles.

A Novel Cr(3+) Fluorescence Turn-On Probe Based on Rhodamine and Isatin Framework.

A novel turn-on fluorescent dye (E)-3',6'-bis(diethylamino)-2-((1-(naphthalen-2-ylmethyl)-2-oxoindolin-3-ylidene)amino)spiro[isoindoline-1,9'-xanthen]-3-one (RBNI) based on a rhodamine-isatin hybrid molecular architecture was synthesized by condensation of isatin derivative with rhodamine hydrazide. The dye RBNI is selective and sensitive for recognition of Cr(3+) ion in aqueous CH3CN media over other tested metal ions. The sensor shows large fluorescence enhancement upon complexation with Cr(3+) and simultaneous color change occurs from colorless to pink-red. Spectroscopic study predicted 1:1 binding stoichiometry between RBNI and Cr(3+) ion and this was again verified through ESI-MS (Electrospray Ionisation Mass Spectrometry). Detection limit of Cr(3+) ion by this dye was calculated to be 2.4 µM. Furthermore, the potential application of this dye for the monitoring of Cr(3+) ions in pond water and tap water samples was demonstrated.

A Novel Mechanochromic and Photochromic Polymer Film: When Rhodamine Joins Polyurethane.

A rhodamine-based molecule, Rh-OH, is synthesized. Rh-OH exhibits a reversible mechanochromic luminescent character but a passivating response to UV light. An elastomeric polymer film based on polyurethane with embedded Rh-OH is prepared via a polycondensation reaction. The film shows mechanochromic and photochromic properties with reversible color change, which originates from the isomerization of the Rh-OH molecule from a twisted spirolactam in the ring-closed form to a planarized zwitterionic structure in the ring-open state.

A core-shell structured inorganic-organic hybrid nanocomposite for Hg(II) sensing and removal.

In the present paper, a core-shell structured inorganic-organic hybrid nanocomposite for Hg(II) sensing and removal was designed and fabricated, where the core was composed of superparamagnetic Fe3O4 and the shell consisted of molecular silica sieve MCM-41. A rhodamine derived probe was grafted onto the backbone of MCM-41 through a silane coupling reagent to control its loading content. This probe functionalized core-shell structure was confirmed and characterized by XRD analysis, electron microscopy images, IR spectra, thermogravimetry and N2 adsorption/desorption isotherms. It was found that the emission of this composite increased with increasing Hg(II) concentrations but was immune to other metal ions, showing good selectivity and high sensitivity towards Hg(II) ions. A linear Stern-Volmer curve was observed with short response time. In addition, this composite possessed good Hg(II)-removing and recycling performance.

A colorimetric and fluorescent turn on chemodosimeter for Pd(2+) detection.

A novel rhodamine derivative L had been successfully developed and well characterized by NMR, and Mass spectroscopy. Chemodosimeter L is a naked-eye fluorescent chemodosimeter for Pd(2+) in aqueous solution. More over the detection limit of Chemodosimeter L is in 10(-7)M level. The Ligand to L ratio was determined to be 1:2 according to the job's plot.

A new rhodamine-based fluorescent chemodosimeter for mercuric ions in water media.

A new rhodamine-ethylenediamine-nitrothiourea conjugate (RT) was synthesized and its sensing property as a fluorescent chemodosimeter toward metal ions was explored in water media. Analytical results from absorption and fluorescence spectra revealed that the addition of Hg(2+) ions to the aqueous solution of the chemodosimeter RT caused a distinct fluorescence OFF-ON response with a remarkable visual color change from colorless to pink; however, no clear spectral and color changes were observed from other metal ions including: Zn(2+) , Cu(2+) , Cd(2+) , Pb(2+) , Ag(+) , Fe(2+) , Cr(3+) , Co(3+) , Ni(2+) , Ca(2+) , Mg(2+) , K(+) and Na(+) . The sensing results and the molecular structure suggested that a Hg(2+) -induced a desulfurization reaction and cyclic guanylation of the thiourea moiety followed by ring-opening of the rhodamine spirolactam in RT are responsible for a distinct fluorescence turn-on signal, indicating that RT is a remarkably sensitive and selective chemodosimeter for Hg(2+) ions in aqueous solution. Hg(2+) within a concentration range from 0.1 to 25 µM can be determined using RT as a chemodosimeter and a detection limit of 0.04 µM is achieved.