Sensitive hydrazine detection and quantification with a fluorescent benzothiadiazole sensor: selective lipid droplets and in vivo imaging.

In this work, we describe the design, synthesis, characterization, photophysical evaluation, DFT calculations, and application of two novel fluorescent benzothiadiazole (BTD) sensors for hydrazine detection and quantification at the cellular and multicellular (in vivo) levels. The two probes were fully characterized, and their photophysical properties were evaluated. We tested the designed fluorogenic dye (named BTD-CHO) as a selective sensor for the rapid, sensitive, and selective detection of hydrazine. When treated with N2H4, the probe affords a new derivative named BTD-HZN, releasing water as the only byproduct. BTD-CHO exhibited a preference for lipid droplets (LDs) and accumulated inside these organelles. Hydrazine detection in LDs could be carried out by the in situ formation of BTD-HZN inside live cells. We efficiently visualized the lipids of a challenging cellular model, microalgae (Chlorella sorokiniana), using these sensors. In vivo experiments indicated rapid and efficient detection of the analyte using C. elegans and zebrafish (Danio rerio) as the multicellular models.

Photocytotoxicity of Thiophene- and Bithiophene-Dipicolinato Luminescent Lanthanide Complexes.

New thiophene-dipicolinato-based compounds, K2nTdpa (n = 1, 2), were isolated. Their anions are sensitizers of lanthanide ion (LnIII) luminescence and singlet oxygen generation (1O2). Emission in the visible and near-infrared regions was observed for the LnIII complexes with efficiencies (ϕLn) ϕEu = 33% and ϕYb = 0.31% for 1Tdpa2- and ϕYb = 0.07% for 2Tdpa2-. The latter does not sensitize EuIII emission. Fluorescence imaging of HeLa live cells incubated with K3[Eu(1Tdpa)3] indicates that the complex permeates the cell membrane and localizes in the mitochondria. All complexes generate 1O2 in solution with efficiencies (ϕO12) as high as 13 and 23% for the GdIII complexes of 1Tdpa2- and 2Tdpa2-, respectively. [Ln(nTdpa)3]3- (n = 1, 2) are phototoxic to HeLa cells when irradiated with UV light with IC50 values as low as 4.2 µM for [Gd(2Tdpa)3]3- and 91.8 µM for [Eu(1Tdpa)3]3-. Flow cytometric analyses indicate both apoptotic and necrotic cell death pathways.

How and Why to Investigate Multicomponent Reactions Mechanisms? A Critical Review.

We review the most innovative efforts and greatest challenges faced when elucidating multicomponent reactions (MCRs) mechanisms. When compared to traditional reactions, the often two or more concurrent reactions pathways and the greater number of possible intermediates in MCRs turn their mechanistic investigation both a harder and trickier task. The common approaches used to investigate reaction mechanisms are often unable to clarify MCRs mechanisms; hence few but clever approaches are currently used to determine these mechanisms and to depict their key transformations. Their complexity has required most innovative approaches and the use of a number of unique techniques that have shed light over the favored pathway selected from the myriad of alternatives theoretically available for MCRs. This review focuses on the most successful efforts applied by a few leading groups to perform these puzzlingly investigations.

Catalytic Approaches to Multicomponent Reactions: A Critical Review and Perspectives on the Roles of Catalysis.

In this review, we comprehensively describe catalyzed multicomponent reactions (MCRs) and the multiple roles of catalysis combined with key parameters to perform these transformations. Besides improving yields and shortening reaction times, catalysis is vital to achieving greener protocols and to furthering the MCR field of research. Considering that MCRs typically have two or more possible reaction pathways to explain the transformation, catalysis is essential for selecting a reaction route and avoiding byproduct formation. Key parameters, such as temperature, catalyst amounts and reagent quantities, were analyzed. Solvent effects, which are likely the most neglected topic in MCRs, as well as their combined roles with catalysis, are critically discussed. Stereocontrolled MCRs, rarely observed without the presence of a catalytic system, are also presented and discussed in this review. Perspectives on the use of catalytic systems for improved and greener MCRs are finally presented.

Review on the Ugi Multicomponent Reaction Mechanism and the Use of Fluorescent Derivatives as Functional Chromophores.

In the present mini-review we discuss the findings, controversies, and gaps observed for the Ugi four-component reaction. The Ugi multicomponent reaction, performed by mixing an aldehyde, an amine, a carboxylic acid, and an isocyanide, is among the most important isocyanide-based multicomponent reactions (MCRs), allowing multiple bond formations (C-C and C-N) in a single synthetic step. The possibility of two reaction pathways and the little understood solvent effect over this transformation renders this reaction as one of the hardest challenges to overcome. The little knowledge of the mechanism of the Ugi MCR hinders the development of new and efficient chiral catalytic systems to further the application of the derivatives obtained by enantioselective versions. The asymmetric transformation is in this context a bigger challenge, and little is known about the mechanism of these few available versions. The new trend of functional chromophore synthesis by MCRs is also highlighted, and the few examples already disclosed in the literature exemplify the huge opportunity for investigation and creative ideas using the Ugi four-component reaction.

Mechanistic knowledge and noncovalent interactions as the key features for enantioselective catalysed multicomponent reactions: a critical review.

This critical review focuses on some key features which determine successful enantioselective catalysed multicomponent reactions (MCRs) and are typically underappreciated in the literature. A critical analysis of this topic is of current interest and the importance of elucidating the reaction mechanism of a MCR, which is usually a neglected task, is a feature of analysis that is aimed at successfully achieving the enantioselective version of the reaction by proper comprehension of the transformation. The key role of noncovalent interactions is another feature analysed along with the transition state (TS) of the key step for the chiral induction of some selected MCRs. In this critical review, the problems of a lack of mechanistic knowledge and the importance of the rational design of new catalytic systems, considering the possible noncovalent interactions aimed towards designing "flexible" and adaptative catalysts to fit the key intermediates and reagents, are discussed in light of new concepts and trends.

Heteropolyacid-Containing Ionic Liquid-Catalyzed Multicomponent Synthesis of Bridgehead Nitrogen Heterocycles: Mechanisms and Mitochondrial Staining.

The current manuscript describes the use of a heteropolyacid-containing task-specific ionic liquid, supported in imidazolium-based ionic liquids, as the catalyst for an efficient multicomponent synthesis of hexahydroimidazo[1,2-α]pyridine derivatives. The reactions conditions were fully optimized, and the bridgehead nitrogen heterocycle derivatives could be obtained in just 1 h exclusively as a single isomer ( trans). Single crystal X-ray analysis confirmed the trans derivative as the only isomer. The mechanism of the reaction was investigated by ESI(+)-MS(/MS), and the use of the elegant charge-tag strategy allowed a catalytic cycle to be proposed for the current transformation and revealed the possibility of at least two reaction pathways. One derivative bearing a coumarin scaffold was synthesized, and its fluorescent properties allowed it to be tested as a probe for live-cell imaging experiments with a preference for mitochondria.

Conversion of "Waste Plastic" into Photocatalytic Nanofoams for Environmental Remediation.

Plastic debris is a major environmental concern, and to find effective ways to reuse polystyrene (PS) presents major challenges. Here, it is demonstrated that polystyrene foams impregnated with SnO2 are easily generated from plastic debris and can be applied to photocatalytic degradation of dyes. SnO2 nanoparticles were synthesized by a polymeric precursor method, yielding specific surface areas of 15 m2/g after heat treatment to 700 °C. Crystallinity, size, and shape of the SnO2 particles were assessed by X-ray diffraction (XRD) and transmission electron microscopy (TEM), demonstrating the preparation of crystalline spherical nanoparticles with sizes around 20 nm. When incorporated into PS foams, which were generated using a thermally induced phase separation (TIPS) process, the specific surface area increased to 48 m2/g. These PS/SnO2 nanofoams showed very good efficiency for photodegradation of rhodamine B, under UV irradiation, achieving up to 98.2% removal. In addition the PS/SnO2 nanofoams are shown to retain photocatalytic activity for up to five reuse cycles.

Inkjet Printing of Lanthanide-Organic Frameworks for Anti-Counterfeiting Applications.

Photoluminescent lanthanide-organic frameworks (Ln-MOFs) were printed onto plastic and paper foils with a conventional inkjet printer. Ln-MOF inks were used to reproduce color images that can only be observed under UV light irradiation. This approach opens a new window for exploring Ln-MOF materials in technological applications, such as optical devices (e.g., lab-on-a-chip), as proof of authenticity for official documents.

Carbon dots (C-dots) from cow manure with impressive subcellular selectivity tuned by simple chemical modification.

Improved cellular selectivity for nucleoli staining was achieved by simple chemical modification of carbon dots (C-dots) synthesized from waste carbon sources such as cow manure (or from glucose). The C-dots were characterized and functionalized (amine-passivated) with ethylenediamine, affording amide bonds that resulted in bright green fluorescence. The new modified C-dots were successfully applied as selective live-cell fluorescence imaging probes with impressive subcellular selectivity and the ability to selectively stain nucleoli in breast cancer cell lineages (MCF-7). The C-dots were also tested in four other cellular models and showed the same cellular selection in live-cell imaging experiments.

Theoretical methodologies for calculation of Judd-Ofelt intensity parameters of polyeuropium systems.

When Judd-Ofelt intensity parameters of polynuclear compounds with asymmetric centers are calculated using the current procedure, the results are inconsistent. The problem arises from the fact that the experimental intensity parameters cannot be determined for each asymmetric polyhedron, and this precludes the individual theoretical adjustment. In this study, we then propose three different methods for calculation of these parameters of polyeuropium systems. The first, named the centroid method, proposes the calculation considering the center of the dimeric system as the half distances between the two europium centers. The second method, called the overlapped polyhedra method, proposes the calculation considering the overlapping of both europium polyhedra, and the last one, the individual polyhedron method, proposes the use of theoretical mean values of charge factors and polarizabilities associated with each europium-ligand atom bond to calculate the intensity parameters. One symmetric polyeuropium system and one asymmetric system were assessed by using the three methods. Among the methods assessed, the one based on the overlapped polyhedra produced more consistent results for the study of both kinds of systems.

Water-soluble Tb3+ and Eu3+ complexes with ionophilic (ionically tagged) ligands as fluorescence imaging probes.

This article describes a straightforward and simple synthesis of ionically tagged water-soluble Eu(3+) and Tb(3+) complexes (with ionophilic ligands) applied for bioimaging of invasive mammal cancer cells (MDA-MB-231). Use of the task-specific ionic liquid 1-methyl-3-carboxymethyl-imidazolium chloride (MAI·Cl) as the ionophilic ligand (ionically tagged) proved to be a simple, elegant, and efficient strategy to obtain highly fluorescent water-soluble Eu(3+) (EuMAI) and Tb(3+) (TbMAI) complexes. TbMAI showed an intense bright green fluorescence emission selectively staining endoplasmic reticulum of MDA-MB-231 cells.

Potential of a metal-organic framework as a new material for solid-phase extraction of pesticides from lettuce (Lactuca sativa), with analysis by gas chromatography-mass spectrometry.

The metal-organic framework (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] was tested for extraction of pyrimicarb, procymidone, malathion, methyl parathion and α- and ß-endosulfan from lettuce, with analysis using GC/MS in SIM mode. Experiments were carried out in triplicate at two fortification levels (0.1 and 0.5 mg/kg), and resulted in recoveries in the range of 78-107%, with RSD values between 1.6 and 8.0% for (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] sorbent. Detection and quantification limits ranged from 0.02 to 0.05 mg/kg and from 0.05 to 0.10 mg/kg, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.05-10.0 µg/mL), with correlation coefficients ranging from 0.9990 to 0.9997. Comparison between (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] and conventional sorbent (silica gel) showed better performance of the (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] polymeric sorbent for all pesticides tested.

Theoretical and experimental spectroscopic approach of fluorinated Ln(3+)-beta-diketonate complexes.

In this paper we report the synthesis of two new complexes, [Eu(fod)(3)(phen)] and [Tb(fod)(3)(phen)] (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadionate and phen = 1,10-phenanthroline), and their complete characterization, including single-crystal X-ray diffraction, UV-vis spectroscopy, IR spectroscopy, and TGA. The complexes were studied in detail via both theoretical and experimental approaches to the photophysical properties. The [Eu(fod)(3)(phen)] complex crystallizes in the monoclinic space group P2(1)/c. The crystal structure of [Eu(fod)(3)(phen)] exhibits an offset pi-pi stacking interaction between the phenanthroline ligands of adjacent lanthanide complexes. The Eu(3+) cation is coordinated to three fod anionic ligands and to one phen. The symmetry around Eu(3+) is best described as a highly distorted square antiprism. The molar absorption coefficients of [Eu(fod)(3)(phen)] and [Tb(fod)(3)(phen)] revealed an improved ability to absorb light in comparison with the stand-alone phen and fod molecules. [Tb(fod)(3)(phen)] emits weak UV excitation, with this feature being explained by the triplet-(5)D(4) resonance, which contributes significantly to the nonradiative deactivation of Tb(3+), causing a short lifetime and low quantum yield. The intensity parameters (Omega(2), Omega(4), and Omega(6)) of [Eu(fod)(3)(phen)] were calculated for the X-ray and Sparkle/AM1 structures and compared with values obtained for [Eu(fod)(3)(H(2)O)(2)] and [Eu(fod)(3)(phen-N-O)] (phen-N-O = 1,10-phenanthroline N-oxide) samples. Intensity parameters were used to predict the radiative decay rate. The theoretical quantum efficiencies from the X-ray and Sparkle/AM1 structures are in good agreement with the experimental values, clearly attesting to the efficacy of the theoretical models.

Modeling, structural, and spectroscopic studies of lanthanide-organic frameworks.

In this paper, we report the hydrothermal synthesis of three lanthanide-organic framework materials using as primary building blocks the metallic centers Eu(3+), Tb(3+), and Gd(3+) and residues of mellitic acid: [Ln(2)(MELL)(H(2)O)(6)] (where Ln(3+) = Eu(3+), Tb(3+), and Gd(3); hereafter designated as (1), (2) and (3)). Structural characterization encompasses single-crystal X-ray diffraction studies, thermal analysis, and vibrational spectroscopy, plus detailed investigations on the experimental and predicted (using the Sparkle/AM1 model) photophysical luminescent properties. Crystallographic investigations showed that the compounds are all isostructural, crystallizing in the orthorhombic space group Pnnm and structurally identical to the lanthanum 3D material reported by the group of Williams. (2) is highly photoluminescent, as confirmed by the measured quantum yield and lifetime (37% and 0.74 ms, respectively). The intensity parameters (Omega(2), Omega(4), and Omega(6)) of (1) were first calculated using the Sparkle/AM1 structures and then employed in the calculation of the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield derived from the Sparkle/AM1 structures was approximately 16%, and the experimental value was 8%. We attribute the registered differences to the fact that the theoretical model does not consider the vibronic coupling with O-H oscillators from coordinated water molecules. These results clearly attest for the efficacy of the theoretical models employed in all calculations and open a new window of interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

Two-dimensional coordination polymer matrix for solid-phase extraction of pesticide residues from plant Cordia salicifolia.

The 2D coordination polymer (infinity[Gd(DPA)(HDPA)]) was tested for extraction of acephate, chlorpropham, pirimicarb, bifenthrin, tetradifon, and phosalone from the medicinal plant Cordia salicifolia, whose extracts are commercialized in Brazil as diuretic, appetite suppressant, and weight loss products, using GC/MS, SIM. Considering that there are no Brazilian regulations concerning maximum permissible pesticide residue concentrations in medicinal herbs, recovery experiments were carried out (seven replicates), at two arbitrary fortification levels (0.5 and 1.0 mg/kg), resulting in recoveries in range of 20 to 107.7% and SDRSDs were between 5.6 and 29.1% for infinity[Gd(DPA)(HDPA)] sorbent. Detection and quantification limits for herb ranged from 0.10 to 0.15 mg/kg and from 0.15 to 0.25 mg/kg, respectively, for the different pesticides studied. The developed method is linear over the range assayed, 0.5-10.0 microg/mL, with correlation coefficients ranging from 0.9975 to 0.9986 for all pesticides. Comparison between infinity[Gd(DPA)(HDPA)] sorbent and conventional sorbent (neutral alumina) showed similar performance of infinity[Gd(DPA)(HDPA)] polymeric sorbent for three (bifenthrin, tetradifon, and phosalone) out of six pesticides tested.

Theoretical and experimental studies of the photoluminescent properties of the coordination polymer [Eu(DPA)(HDPA)(H2O)2].4H2O.

We report on the hydrothermal synthesis of the [Eu(DPA)(HDPA)(H(2)O)(2)].4H(2)O lanthanide-organic framework (where H2DPA stands for pyridine-2,6-dicarboxylic acid), its full structural characterization including single-crystal X-ray diffraction and vibrational spectroscopy studies, plus detailed investigations on the experimental and predicted (using the Sparkle/PM3 model) photophysical luminescent properties. We demonstrate that the Sparkle/PM3 model arises as a valid and efficient alternative to the simulation and prediction of the photoluminescent properties of lanthanide-organic frameworks when compared with methods traditionally used. Crystallographic investigations showed that the material is composed of neutral one-dimensional coordination polymers infinity(1)[Eu(DPA)(HDPA)(H(2)O)(2)] which are interconnected via a series of hydrogen bonding interactions involving the water molecules (both coordinated and located in the interstitial spaces of the structure). In particular, connections between bilayer arrangements of infinity(1)[Eu(DPA)(HDPA)(H(2)O)(2)] are assured by a centrosymmetric hexameric water cluster. The presence of this large number of O-H oscillators intensifies the vibronic coupling with water molecules and, as a consequence, increases the number of nonradiative decay pathways controlling the relaxation process, ultimately considerably reducing the quantum efficiency (eta = 12.7%). The intensity parameters (Omega(2), Omega(4), and Omega(6)) were first calculated by using both the X-ray and the Sparkle/PM3 structures and were then used to calculate the rates of energy transfer (W(ET)) and back-transfer (W(BT)). Intensity parameters were used to predict the radiative decay rate. The calculated quantum yield obtained from the X-ray and Sparkle/PM3 structures (both of about 12.5%) are in good agreement with the experimental value (12.0 +/- 5%). These results clearly attest for the efficacy of the theoretical models employed in all calculations and create open new interesting possibilities for the design in silico of novel and highly efficient lanthanide-organic frameworks.

Design of europium(III) complexes with high quantum yield.

This work describes a rational planning of a new light-conversion molecular device with high quantum yield. For this, we made modifications in the 3-amino-2-carboxypyridine and 3-amino-2-carboxypirazine acid ligands, generating eight different complexes. Theoretical methods have been used to calculate the quantum yield of each of the complexes. We first used the Sparkle model to calculate the ground-state geometries of the eight complexes. These data were used to perform theoretical predictions of the energy transitions using the INDO/S-CI method. After having obtained the geometry and the energy transitions, the energy transfer rates and quantum yield were calculated using a theoretical approach based on the application of the 4f-4f transition theory. The results show that the modifications in the 3-amino-2-carboxypyridine ligand had generated three complexes with high quantum yield (about 52.8, 51.6 and 52.8%). On the other hand, the modifications in the 3-amino-2-carboxypirazine led to only one complex with quantum yield larger than 50%, but it is the most efficient complex projected.