Disorder-Enhanced Charge-Transfer-Mediated Room-Temperature Phosphorescence in Polymer Media

Room-temperature phosphorescence (RTP) polymers have important applications for biological imaging, oxygen sensing, data encryption, and photodynamic therapy. Despite the many advantages polymeric materials offer such as great control over gas permeability and processing flexibility, disorder is traditionally considered as an intrinsic negative impact on the efficiency for embedded RTP luminophores, as various allowed thermal motions could quench the emitting states. However, we propose that such disorder-enabled freedoms of microscopic motions can be beneficial for charge-transfer-mediated RTP, which is facilitated by molecular conformational changes among different electronic transition states. Using the “classic” pyrene-aniline exciplex as an example, we demonstrate the mutual enhancement of red/near-infrared and green RTP emissions from the pyrene and aniline moieties, respectively, upon doping the aniline polymer with trace pyrene derivatives. In comparison, a pyrene-doped crystal formed with the same aniline structure exhibits only charge-transfer fluorescence with no red or green RTP observed, suggesting that order suppresses the RTP channels. The proposed polymerization strategy may be used as a unified method to generate multi-emissive polymeric RTP materials from a vast pool of known and unknown exciplexes and charge-transfer complexes.     

Study of properties on non-protected room temperature phosphorescence and delayed excimer fluorescence of pyrene solution

A strong and stable room temperature phosphorescence (RTP) and delayed excimer fluorescence signal located at 596 and 475 nm, respectively, can be induced for pyrene solution in the absence of any protective medium only use KI or TlNO3 as a heavy atom perturber (HAP) and Na2SO3 as a deoxygenator. Both lifetimes of RTP and the delayed fluorescence are in the order of X-ms and the intensities are changed with kind and amount of HAP, but the peak positions are same and there is a iso-luminescent point in the emission spectra corresponding to emission at 475 nm and at 596 nm. The optimum conditions and the effects of kind and amount of HAP and organic solvents on luminescence properties of pyrene solution were studies in detail, and the photophysical process in the presence of KI or TlNO3 for phosphorescence and delayed excimer fluorescence emission of pyrene solution was discussed.     

New approach for screening polycyclic aromatic hydrocarbons in water samples

For the first time, solid-phase extraction (SPE) has been combined to room-temperature phosphorimetry (RTP) to determine the 16 polycylic aromatic hydrocarbons related as major pollutants by the US Environmental Protection Agency (EPA). These include naphthalene, anthracene, acenaphthylene, acenaphthene, fluorene, fluoranthene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, pyrene, chrysene, phenanthrene, benzo(g,h,i)perylene and dibenzo(a,h)anthracene. The pre-concentration factor obtained by SPE, combined with the sensitivity of RTP, resulted in calibration curves with linear dynamic ranges at the parts-per-billion level (ng ml(-1)). The limits of detection were estimated at the parts-per-trillion level (pg ml(-1)). Several pollutants usually encountered in water samples were tested for interference. These included polychlorinated biphenyls, pesticides, and volatile organic compounds. As a result of the appropriate combination of excitation wavelength (330 nm) and phosphorescence enhancers (0.1 M TlNO(3) and 0.05 M sodium dodecyl sulfate, SDS), no interference was observed. The results demonstrate the potential of SPE-RTP for screening polycyclic aromatic hydrocarbons (PAHs) in environmental waters.     

Room temperature phosphorescence optosensing of benzo[a]pyrene in water using halogenated molecularly imprinted polymers

A selective optosensor for benzo[a]pyrene (BaP) determination in water samples, using a molecularly imprinted polymer (MIP) for the recognition of the analyte, has been developed. Detection was based on measurements of the native strong room temperature phosphorescence (RTP) emission from the BaP recognized by the MIP. The non-covalent MIP was synthesized using BaP as a molecular template. Different halogenated-bisphenol A compounds were compared as precursors in the polymerization (thus ensuring the presence of a heavy atom, required to induce RTP emission from the analyte). In the developed optosensor, samples are injected in a flow system and the analyte is on-line retained onto the polymeric material. In the absence of oxygen (using sodium sulfite as the oxygen scavenger) the heavy atom present in the MIP structure induced analytically useful RTP emission from the recognized BaP. After measurement of the luminescent emission, the sensing material can be easily regenerated by passing 2 mL of methanol over the MIP. The optosensor demonstrated a very high selectivity for BaP determination in water even in the presence of other luminophores that could be non-specifically adsorbed onto the MIP surface. Under optimal experimental conditions, a benzo[a]pyrene detection limit of 10 ng L(-1) (20 mL sample injection volume) was achieved with good reproducibility (a RSD of 3% was obtained for 1 microg L(-1) BaP). Finally, the proposed optosensor was successfully applied to the analysis of spiked natural water with BaP.     

Using Room Temperature Phosphorescence of Gold(I) Complexes for PAHs Sensing

The synthesis of two new phosphane-gold(I)–napthalimide complexes has been performed and characterized. The compounds present luminescent properties with denoted room temperature phosphorescence (RTP) induced by the proximity of the gold(I) heavy atom that favors intersystem crossing and triplet state population. The emissive properties of the compounds together with the planarity of their chromophore were used to investigate their potential as hosts in the molecular recognition of different polycyclic aromatic hydrocarbons (PAHs). Naphthalene, anthracene, phenanthrene, and pyrene were chosen to evaluate how the size and electronic properties can affect the host:guest interactions. Stronger affinity has been detected through emission titrations for the PAHs with extended aromaticity (anthracene and pyrene) and the results have been supported by DFT calculation studies.     

Acridine dyes in the triplet state as reagents for the selective luminescence determination of polycyclic aromatic hydrocarbons

The possibility of the selective determination of several polycyclic aromatic hydrocarbons (PAH) by sensitized room-temperature phosphorescence (SRTP) in sodium dodecylsulfate (SDS) micelles was studied. Acridine dyes (trypaflavine, acridine yellow, and acridine orange) were used as triplet-energy donors. It was found that the presence of external heavy atoms of thallium(I) is a prerequisite to SRTP in the system of an acridine dye (donor) and a PAH (acceptor). The linear concentration ranges, detection limits, and selectivity factors for the determination of pyrene, anthracene, and 1,2-benzanthracene by fluorimetry, room-temperature phosphorescence (RTP), and proposed SRTP were compared.     

Luminescence Properties and Analytical Figures of Merits of Benzo(a)Pyrene Guanosine Adduct Adsorbed on α- β- and γ-Cyclodextrin/NaCl,and Trehalose/NaCl Solid Matrices

Abstract

Several cyclodextrin/NaCl and trehalose/NaCl mixtures were investigated as solid matrices for obtaining room-temperature luminescence from a benzo(a)pyrene (B(a)P) guanosine adduct. Room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) intensities from the B(a)P-guanosine adduct were compared for different solid matrices. These results showed that 25% trehalose/NaCl, 1% α-cyclodextrin/NaCl, and 1% γ-cyclodextrin/NaCl solid matrices yielded strong fluorescence signals and moderately strong phosphorescence signals at room temperature from the B(a)P-guanosine adduct. In addition, the luminescence properties of pyrene, guanosine, guanosine 3′ -monophosphate free acid and guanosine 3′-monophosphate sodium salt on 1% α-, β-, and γ- cyclodextrin/NaCl solid matrices were obtained.     

Carbon dots confined in 3D polymer network: Producing robust room temperature phosphorescence with tunable lifetimes

Room temperature phosphorescence(RTP) is important in both organic electronics and encryption. Despite rapid advances, a universal approach to robust and tunable RTP materials based on amorphous polymers remains a formidable challenge. Here, we present a strategy that uses three-dimensional(3 D)confinement of carbon dots in a polymer network to achieve ultra-long lifetime phosphorescence. The RTP of the as-obtained materials was not quenched in different polar organic solvents and the lifetime o...     

Visible-light-excited long-lived organic room-temperature phosphorescence of phenanthroline derivatives in PVA matrix by H-bonding interaction for security applications

Organic room-temperature phosphorescence (RTP) materials are very attractive, but there is still a challenge to achieve RTP for their practical applications under visible light excitation (λ > 400 nm) because of the implement for the most organic RTP is under ultraviolet light. Herein, a simple tactics for inhibiting the vibrational dissipation of three amorphous phenanthroline derivatives by doping them into polyvinyl alcohol (PVA) matrix was utilized to afford visible-light excitation RTP. By using this method, on account of the mutual H-bonding and confinement effect with PVA matrix, a series of organic RTP materials with blue-green phosphorescence emission were obtained under visible-light excitation. The afterglow colors of RTP materials can be adjusted by co-doping the available fluorescence dyes (RhB or Rh6G) into the PVA films through a triplet-to-singlet Förster resonance energy transfer. However, the H-bonding is easily broken by water molecules resulting in the RTP phenomenon disappears. Hence, Aphen-epoxy resin composite system was constructed to overcome this drawback. It is shown that the composite still has good phosphorescence properties after soaking in water for 7 days. The superior RTP of the amorphous phenanthroline derivatives in processable polymer matrices endows these materials with a highly potential for the night warning clothing coating and information encryption.     

Characterization of transition metal nitride formation in rapid thermal processing (RTP)

The potential of RTP for the preparation of transition metal nitrides by reaction of metal thin films in molecular nitrogen was investigated. The films and the nitridation process were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive x-ray analysis (EDX) in a scanning electron microscope (SEM) and secondary neutral mass spectrometry (SNMS). The chemical states of vanadium at the utmost surface, detected by XPS, are related to V₂O₅ before RTP and to vanadium nitride, oxide and oxynitride after RTP. The deposition of a 3 nm Si top layer prevents V from oxidation and its selective removal before RTP enhances the proportion of nitride determined by XPS after RTP. From comparative experiments in a conventional tube furnace the advantages of RTP became obvious. With short process times of the RTP technique the integral amount of residual oxygen is kept low and oxide formation is largely avoided. The nitrogen content and the different polycrystalline phases formed by varying process time and temperature provide information about reactivity and the nitridation process. The nitrogen to vanadium ratio was determined by EDX and SNMS, revealing that the N content reaches saturation after only 5 seconds at 1100?°C.     

Oxygen sensor via the quenching of room-temperature phosphorescence of perdeuterated phenanthrene adsorbed on Whatman 1PS filter paper

Perdeuterated phenanthrene (d-phen) exhibits strong room-temperature phosphorescence (RTP) when adsorbed on Whatman 1PS filter paper. An oxygen sensor was developed that depends on oxygen quenching of RTP intensity of adsorbed d-phen. The system designed employed a continuous flow of nitrogen or nitrogen-air onto the adsorbed phosphor. The sensor is simple to prepare and needs no elaborate fabrication procedure, but did show a somewhat drifting baseline for successive determinations of oxygen. Nevertheless, very good reproducibility was achieved with the RTP quenching data by measuring the RTP intensities just before and at the end of each oxygen determination. The calibration plots gave a nonlinear relationship over the entire range of oxygen (0-21%). However, a linear range was obtained up to 1.10% oxygen. A detection limit of 0.09% oxygen in dry nitrogen was acquired. Also, carbon dioxide was found to have a minimal effect on the RTP quenching. Thus, oxygen could be measured accurately in relatively large amounts of carbon dioxide. The performance of the oxygen sensor was evaluated by comparing data obtained with a commercial electrochemical trace oxygen analyzer. Also, additional information on the quenching phenomena for this system was obtained from the RTP lifetime data acquired at various oxygen contents.     

Synchronous wavelength scanning room temperature phosphorescence: Comparison of cyclodextrin and micellar media

Application of synchronous wavelength scanning to two fluid phase room temperature phosphorescence (RTP) techniques using β-cyclodextrin and micelles are evaluated and compared. The selectivity, sensitivity, susceptibility to light scattering interference and classes of compounds amenable to determination by the two RTP approaches are discussed. Synchronous wavelength scanning cyclodextrin RTP studies focus on its usefulness for identification of nitrogen heterocyclic phosphors. Spectral resolution is improved in both RTP techniques by second derivative manipulation of the digitally stored synchronous spectra. A significant scatter interference resulting from turbidity produced by the cyclodextrin inclusion complexes imposes constraints on the selectivity and sensitivity achievable with the cyclodextrin medium, especially when using synchronous wavelength scanning. Generally, micelle-induced RTP was found to be superior to cyclodextrin-induced RTP for analysis of various mixtures of the 12 heterocyclics and 15 carbocyclics studied, as well as for a mixture of the drug, propranolol, and its 4-hydroxy metabolite.     

Enhanced room temperature phosphorescence of palladium‐porphyrin by dual‐ordered structure of micelle‐hybridized supramolecular gels

Meso‐tetra (carbonyl phenyl) porphyrin palladium (denoted as Pd‐TCPP), a typical organometallic compound, was used as phosphor and entrapped in micelle‐hybridized supramolecular hydrogels. As a novel matrix material of phosphors, the hybrid system was comprised of two ordered structures: a supramolecular 3D network structure formed by the self‐assembly of the gelator and the micelles formed from a Gemini surfactant. The dual‐ordered structure of the system was verified by SEM, TEM and fluorescent optical microscopy. By contrast with corresponding mono‐ordered structure, the room temperature phosphorescence (RTP) of Pd‐TCPP was greatly enhanced by the dual‐ordered structure of the system. The enhancement mechanism of RTP was studied by hydrophobicity of the system, RTP quenching and disassembly of supramolecular aggregates. Enhanced RTP could be attributed to the efficient inhibition of the non‐radiative transition of Pd‐TCPP by dual‐ordered structures. Significantly, the RTP intensity of Pd‐TCPP can be adjusted by changing the concentration of Gemini surfactants. Furthermore, deoxygenation was not required in this hybrid system in comparison with corresponding mono‐component systems.     

Carbon Dots with Dual-Emissive,Robust, and Aggregation-Induced Room-Temperature Phosphorescence Characteristics

Carbon dots (CDs) with dual-emissive, robust, and aggregation-induced RTP characteristics are reported for the first time. The TA-CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA-CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual-emissive nature. The RTP emission of TA-CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA-CDs, advanced anti-counterfeiting and information encryption methodologies (water-stimuli-response producing RTP) were preliminarily investigated.     

Direct and rapid discrimination of aflatoxigenic strains based on fibre-optic room temperature phosphorescence detection

An innovative analytical methodology for the rapid identification of aflatoxin-producing moulds belonging to Aspergillus genus is presented here. The procedure is based on the measurement, using a fibre-optic luminometer, of the room temperature phosphorescence (RTP) emitted by aflatoxins produced by isolated aflatoxigenic strains, cultured in a special culture medium consisting of malt extract agar modified with beta-cyclodextrin and sodium deoxycholate for RTP induction. Unequivocal detection of the presence of aflatoxins in the culture medium is achieved within the first 36 h of incubation at 32 degrees C, owing to the selectivity and sensitivity of the RTP emission, as compared with the minimum of 72 h needed using a conventional microbiological method. In a first step, the capability of aflatoxin standard solutions to emit analytically useful RTP was evaluated. In this line all experimental conditions were optimised for in vitro induction of RTP from aflatoxins. In a second step, a simple analytical test was developed and it has been evaluated for the rapid identification of aflatoxigenic strains, as a discriminating assay from non-aflatoxigenic strains based on the measurement of experimental RTP emission observed. Confirmation of aflatoxin production on the studied culture plates was accomplished by means of an HPLC/fluorescence reference method.     

Carbon Dots with Dual‐Emissive,Robust, and Aggregation‐Induced Room‐Temperature Phosphorescence Characteristics

Carbon dots (CDs) with dual‐emissive, robust, and aggregation‐induced RTP characteristics are reported for the first time. The TA‐CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA‐CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual‐emissive nature. The RTP emission of TA‐CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA‐CDs, advanced anti‐counterfeiting and information encryption methodologies (water‐stimuli‐response producing RTP) were preliminarily investigated.     

An Unexpected Chromophore–Solvent Reaction Leads to Bicomponent Aggregation-Induced Phosphorescence

Organic luminogens with persistent room-temperature phosphorescence (RTP) have found a wide range of applications. However, many RTP luminogens are prone to severe quenching in the crystalline state. Herein, we report a strategy to construct a donor-sp³-acceptor type luminogen that exhibits aggregation-induced emission (AIE) while the donor-sp²-acceptor counterpart structure exhibits a non-emissive solid state. Unexpectedly, it was discovered that a trace amount (0.01 %) of the structurally similar derivative, produced by a side reaction with the DMF solvent, could induce strong RTP with an absolute RTP yield up to 25.4 % and a lifetime of 48 ms, although the substance does not show RTP by itself. Single-crystal XRD-based calculations suggest that n–σ* orbital interactions as a result of structural similarity may be responsible for the strong RTP in the bicomponent system. This study provides a new insight into the design of multi-component, solid-state RTP materials from organic molecular systems.     

Determination of photophysical rate constants for the non-protected fluid room temperature phosphorescence of several naphthalene derivatives.

The determination of kinetic parameters for luminescence processes is very important in understanding the phosphorescence process and the mechanisms of the heavy atom effect (HAE). In our previous work, we reported that room temperature phosphorescence (RTP) emission of many naphthalene derivatives can be induced directly from their aqueous solution without using any kind of protective medium, and the name Non-Protected Fluid Room Temperature Phosphorescence (NP-RTP) is suggested for this new type of RTP emission. In order to further understand this kind of luminescence phenomenon, the influence of heavy atom perturber (HAP) concentration on RTP lifetime of several naphthalene derivatives was studied in detail in this paper. The possibility of determination of photophysical parameters for emission of NP-RTP was explored based on the definition on the phosphorescence lifetime and the relation with the concentration of HAP in this paper. A static Stern-Volmer equation for phosphorescence was derived and the luminescence kinetic parameters were calculated. The results obtained by two different ways proved that photophysical parameters for RTP emission can be determined based on the changes of the RTP lifetime.     

An Unexpected Chromophore–Solvent Reaction Leads to Bicomponent Aggregation‐Induced Phosphorescence

Organic luminogens with persistent room‐temperature phosphorescence (RTP) have found a wide range of applications. However, many RTP luminogens are prone to severe quenching in the crystalline state. Herein, we report a strategy to construct a donor‐sp³‐acceptor type luminogen that exhibits aggregation‐induced emission (AIE) while the donor‐sp²‐acceptor counterpart structure exhibits a non‐emissive solid state. Unexpectedly, it was discovered that a trace amount (0.01 %) of the structurally similar derivative, produced by a side reaction with the DMF solvent, could induce strong RTP with an absolute RTP yield up to 25.4 % and a lifetime of 48 ms, although the substance does not show RTP by itself. Single‐crystal XRD‐based calculations suggest that n–σ* orbital interactions as a result of structural similarity may be responsible for the strong RTP in the bicomponent system. This study provides a new insight into the design of multi‐component, solid‐state RTP materials from organic molecular systems.     

The Effect of Molecular Conformations and Simulated “Self-Doping” in Phenothiazine Derivatives on Room-Temperature Phosphorescence

The research of purely organic room-temperature phosphorescence (RTP) materials has drawn great attention for their wide potential applications. Besides single-component and host–guest doping systems, the self-doping with same molecule but different conformations in one state is also a possible way to construct RTP materials, regardless of its rare investigation. In this work, twenty-four phenothiazine derivatives with two distinct molecular conformations were designed and their RTP behaviors in different states were systematically studied, with the aim to deeply understand the self-doping effect on the corresponding RTP property. While the phenothiazine derivatives with quasi-axial (ax) conformation presented better RTP performance in aggregated state, the quasi-equatorial (eq) ones were better in isolated state. Accordingly, the much promoted RTP performance was achieved in the stimulated self-doping state with ax-conformer as host and eq-one as guest, demonstrating the significant influence of self-doping on RTP effect.