Phosphorescence from pyrimidine vapor

The phosphorescence from pyrimidine vapor has been observed by a method of time-resolved laser spectroscopy. The phosphorescence spectrum commences at 350.5 nm and consists mainly of three totally symmetric vibrations in the ground state, v_6a, v₁₂ and v_9a as in the case of the zero-point vibrational level fluorescence of pyrimidine vapor. The phosphorescence quantum yield and lifetime are found to be about 1 × 10^?4 and 50 μs.     

Fast and slow deposition of silver nanorods on planar surfaces: application to metal-enhanced fluorescence

Two methods have been considered for the deposition of silver nanorods onto conventional glass substrates. In the first method, silver nanorods were deposited onto 3-(aminopropyl)triethoxysilane-coated glass substrates simply by immersing the substrates into the silver nanorod solution. In the second method, spherical silver seeds that were chemically attached to the surface were subsequently converted and grown into silver nanorods in the presence of a cationic surfactant and silver ions. The size of the silver nanorods was controlled by sequential immersion of silver seed-coated glass substrates into a growth solution and by the duration of immersion, ranging from tens of nanometers to a few micrometers. Atomic force microscopy and optical density measurements were used to characterize the silver nanorods deposited onto the surface of the glass substrates. The application of these new surfaces is for metal-enhanced fluorescence (MEF), whereby the close proximity of silver nanostructures can alter the radiative decay rate of fluorophores, producing enhanced signal intensities and an increased fluorophore photostability. In this paper, it is indeed shown that irregularly shaped silver nanorod-coated surfaces are much better MEF surfaces as compared to traditional silver island or colloid films. Subsequently, these new silver nanorod preparation procedures are likely to find a common place in MEF, as they are a quicker and much cheaper alternative as compared to surfaces fabricated by traditional nanolithographic techniques.     

Photosystem II fluorescence: slow changes--scaling from the past

With the advent of photoelectric devices (photocells, photomultipliers) in the 1930s, fluorometry of chlorophyll (Chl) a in vivo emerged as a major method in the science of photosynthesis. Early researchers employed fluorometry primarily for two tasks: to elucidate the role in photosynthesis, if any, of other plant pigments, such as Chl b, Chl c, carotenoids and phycobilins; and to use it as a convenient inverse measure of photosynthetic activity. In pursuing the latter task, it became apparent that Chl a fluorescence emission is influenced (i) by redox active Chl a molecules in the reaction center of photosystem (PS) II (photochemical quenching); (ii) by an electrochemical imbalance across the thylakoid membrane (high energy quenching); and (iii) by the size of the peripheral antennae of weakly fluorescent PSI and strongly fluorescent PSII in response to changes in the ambient light (state transitions). In this perspective we trace the historical evolution of our awareness of these concepts, particularly of the so-called 'State Transitions'.     

Fluorescence polarization and intramolecular vibrational redistribution in pyrimidine vapor

The fluorescence emitted from the initially prepared vibronic level (IPL) in S₁ of pyrimidine vapor is polarized and the degree of polarization varies remarkably for excitation along the rotational contour of various vibronic absorption bands, whereas the broad fluorescence emitted from levels to which the molecule is transferred from the IPL as a result of intramolecular vibrational redistribution (IVR) is nearly depolarized. On the basis of these results, the role of molecular rotation in IVR is discussed.     

Dual fluorescence lifetimes of pyrimidine: Intermediate radiationless decay

We have observed a dual fluorescence decay from the lowest n → π* excited singlet state of pyrimidine. The vibronic states 0-0, 6a¹, 12¹, 6a¹12¹, 12² and 6a¹12² have two exponential decays with lifetimes ranging from 2.7-0.7 nsec and from 410-234 ns at 0.02 torr. The ratio of pre-exponentials is pressure independent but the long decay is very sensitive to collisions. The four lower energy states have effective impact diameters of 16 A and the highest energy state is quenched by gas kinetic collision diameters (≈ 5.5 Å). The dual fluorescence decay and collisional fluorescence quenching by rotational relaxation is consistent with the available models of singlet-triplet mixed state decay. Using these models we have computed the rates for singlet-triplet crossing, the number of coupled triplet levels, and the decay rates for internal conversion. The model used our measured fluorescence decay parameters and our estimate of a triplet loss rate. The estimated triplet loss varies from 0.2 to 2.0 × 10⁶ s^?1 and the singlet internal conversion rate varies from ≈ 0.4 to 56 × 10⁷ s^?1. The singlet-triplet radiationless rate suggests that 50–100 times more triplet levels are effective in the state mixing than can be expected from the triplet vibronic density. Such an enhanced coupling of ro-vibronic triplet levels is 5–10 times larger than previously observed for the dicarbonyls. The observation of reduced collisional quenching of higher energy vibronic levels is quantitatively interpreted by a different model than used previously for the dicarbonyls.     

Development of vapor phase decomposition-total-reflection X-ray fluorescence spectrometer

A total reflection X-ray fluorescence spectrometer integrated with vapor phase decomposition, VPD-TXRF, was newly developed. This instrument was designed to achieve a minimum footprint, to avoid cross contamination during operation, and to protect people and instruments from HF gas. Comparisons between analysis by VPD-TXRF and by atomic absorption spectrometry (AAS) indicated very good agreement in a wide range, from 10⁸ to 10¹² atoms/cm². The lower limits of detection (LLDs) were improved by two orders of magnitude compared with straight TXRF. For 300-mm Si wafers, the LLDs were 5×10⁸ atoms/cm² and 1×10⁷ atoms/cm² for Al and Ni, respectively. VPD-TXRF was able to perform ultra-trace analysis at the level of 10⁸ atoms/cm².     

Fast and stable photochromic oxazines for fluorescence switching

The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level.     

Fast fluorescence switching within hydrophilic supramolecular assemblies

We designed a supramolecular strategy to modulate fluorescence in water under optical control. It is based on the entrapment of fluorophore-photochrome dyads within the hydrophobic interior of an amphiphilic polymer. The polymeric envelope around the dyads protects them from the aqueous environment, while imposing hydrophilic character on the overall supramolecular construct. In the resulting assemblies, the photochromic component can be operated reversibly on a microsecond timescale under the influence of ultraviolet stimulations. In turn, the reversible transformations control the emission intensity of the adjacent fluorophore. As a result, the fluorescence of such nanostructured constructs can be photomodulated for hundreds of cycles in water with microsecond switching speeds. Thus, our protocol for fast fluorescence switching in aqueous solutions can eventually lead to the realization of functional probes for the investigation of biological samples.     

UV light-emitting-diode photochemical mercury vapor generation for atomic fluorescence spectrometry

A new, miniaturized and low power consumption photochemical vapor generation (PVG) technique utilizing an ultraviolet light-emitting diode (UV-LED) lamp is described, and further validated via the determination of trace mercury. In the presence of formic acid, the mercury cold vapor is favourably generated from Hg(2+) solutions by UV-LED irradiation, and then rapidly transported to an atomic fluorescence spectrometer for detection. Optimum conditions for PVG and interferences from concomitant elements were investigated in detail. Under optimum conditions, a limit of detection (LOD) of 0.01 μg L(-1) was obtained, and the precision was better than 3.2% (n = 11, RSD) at 1 μg L(-1) Hg(2+). No obvious interferences from any common ions were evident. The methodology was successfully applied to the determination of mercury in National Research Council Canada DORM-3 fish muscle tissue and several water samples.     

Fast and slow processes of thermal deactivation of excited stilbazolium merocyanine dyes

The long living triplet states play important role in sensitizing action in all photochemical reactions. The yield of generation of triplet states of dyes can be evaluated on the basis of measurements of their slow (microsecond) thermal deactivation (TD). All experiments were carried out in the oxygen presence, it means under quenching dye triplets. The pulse dye laser generates in the investigated solution pressure signal. The high of the amplitudes of first maximum of this pressure wave-form signal in the solution of the investigated dye and in the reference sample were measured. Reference sample exhibits only fast processes of TD. The comparison of the first maximum of wave-form photothermal signal of sample and of reference enable to calculate part of energy exchanged into heat in time longer than time resolution of arrangement. The fluorescence yields of investigated dyes were also established. On the basis of such data, using procedure described in literature, the yield of singlet–triplet intersystem crossing (ISC) was evaluated. It was shown that this yield depends on the length of stilbazolium merocyanine chain. The product of triplet state yield and energy was lower for merocyanines with longer chains. At lower temperatures the yield of fluorescence increases and amount of excitation exchanged in short time into heat decreases. The slow TD process increases in low temperature because of the decrease in the quenching of the dyes triplet states by oxygen. The amount of energy exchanged into heat in a time longer than time resolution of apparatus is due predominantly through TD of the dye triplet states.     

Rotational effects on the quantum yield and lifetime of the slow component of fluorescence from s-triazine

The fluorescence quantum yield and lifetime of the slow component of fluorescence obtained along the rotational contour of the 6¹₀ and 6²₀ absorption bands of s-triazine at low pressure show a marked variation. For each band, the quantum-yield spectrum shows a sharp peak at the Q-branch edge, the lifetime spectrum exhibits a valley at the same position.     

Fast and high yield post-synthetic modification of metal-organic frameworks by vapor diffusion

Vapor-phase post-synthetic modification (VP-PSM) is herein described. VP-PSM is a tool that overcomes limitations of standard PSM methods by giving a higher yield in short reaction times and will give more flexibility in designing metal-organic frameworks with functionalization for chemical and physical applications.     

Trisubstituted pyrimidine derivatives from tetrafluoropyrimidine

The use of tetrafluoropyrimidine as a scaffold for the synthesis of 2,4,6-trisubstituted pyrimidine derivatives by three sequential nucleophilic aromatic substitution processes is assessed. Reactions of tetrafluoropyrimidine with various amine nucleophiles followed by a series of nitrogen and oxygen centred nucleophilic species gave a range of 4,6-disubstituted-2,5-difluoropyrimidine systems regioselectively and in good yield. Displacement of a further fluorine atom from representative difluoropyrimidine derivatives proceeded to give trisubstituted pyrimidine derivatives although mixtures of products could be obtained depending upon the substrate.     

Fast annealing and patterning of polymer solar cells by means of vapor printing

The viability of vapor printing as a fast annealing treatment for the processing of polymer solar cells is demonstrated. In this method, a carrier gas transporting vapor solvent is delivered through a nozzle promoting self‐assembly of polymer chains. Devices based on poly(3‐hexylthiophene) blended with soluble fullerene are locally exposed during different annealing times to chlorobenzene vapor in a nitrogen flow. This enables finding an optimal nanostructure in promisingly short time‐scales (<5 s of exposure to vapor solvent), which yields a twofold increase in efficiency with respect to as‐cast samples. Moreover, a combined Raman, photometric, and ellipsometric characterization allows to understand why overexposure to vapor solvent reduces the performance. Finally, toluene and 1,2,3,4‐tetrahydronaphthalene are also tested using this method, showing different printing efficiencies corresponding to their specific vapor pressures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis,spectral, fluorescence,thermal and biological studies on ionic hafnocene pyrimidine complexes

Ionic chelates of hafnocene with uracil (HL¹) (A) and 5-fluorouracil (HL²) (B) of the type [(⁵- C₅H₅)₂HfL¹]⁺X^– (C) and [(⁵- C₅H₅)₂HfL²]⁺X^– (D) (X = CuCl₃, ZnCl₃, CdCl₃, HgCl₃, PhNHNHCS₂) have been prepared and characterised by conductivity measurements and by i.r., electronic, ¹H-n.m.r. and ¹³C-n.m.r. spectra. Fluorescence studies of the complexes containing Hg in the anionic moiety, and relevant photochemical parameters, have been elucidated. Thermodynamic parameters have been calculated using thermogravimetric (t.g.) and differential thermal analytical (d.t.a.) curves, and their variations have been correlated with some structural parameters of the complexes. The ligands, as well as their hafnium(IV) complexes, exhibit appreciable antibacterial and antifungal activity against E. coli, S. typhi, P. aeruginosa and Z. mobilis bacterial strains, and versus A. awamori and A. niger fungal strains, respectively.     

Comparison of direct-total-reflection X-ray fluorescence,sweeping-total-reflection X-ray fluorescence and vapor phase decomposition-total-reflection X-ray fluorescence applied to the characterization of metallic contamination on semiconductor wafers

The issues related to the matching between the 3 modes of Total-reflection X-Ray Fluorescence available on the latest generation of commercial equipment: Direct-Total-reflection X-Ray Fluorescence, Sweeping-Total-reflection X-Ray Fluorescence and Vapor Phase Decomposition-Total-reflection X-Ray Fluorescence, are discussed for quantitative analysis of metallic contamination on Si wafers. Direct-Total-reflection X-Ray Fluorescence and Sweeping-Total-reflection X-Ray Fluorescence agrees very well (+/− 20% for light elements, transition metals and heavy metals), but due to a poor surface coverage with Direct-Total-reflection X-Ray Fluorescence, the matching is correct on a whole wafer only for uniform contaminations. Vapor Phase Decomposition-Total-reflection X-Ray Fluorescence might agree with other Total-reflection X-Ray Fluorescence modes only if the collection of contaminants following the oxide decomposition step is 100% completed. This is not achieved for 2 situations: noble metals which plate on bare Si, and solid particles partially digested during the Vapor Phase Decomposition and collection protocol. Furthermore, even if the collection of contaminants is well completed, quantification after Vapor Phase Decomposition depends on the shape of the dried residues and the Total-reflection X-Ray Fluorescence incident angle. With the incident angle selected to maximize the signal to noise ratio for ultra trace applications, i.e. about 0.5 times the Si critical angle, an increase of the quantification by a factor up to 10 is often seen after Vapor Phase Decomposition because of particle-like shape of the metals against film-like shape for the initial distribution. Taking into account advantages and drawbacks of each Total-reflection X-Ray Fluorescence mode, a proposal for the use of Total-reflection X-Ray Fluorescence in advanced Integrated Circuit manufacturing is given and illustrated by practical results from a R&D pilot line and a mass production plant.     

An examination of the vaporization enthalpies and vapor pressures of pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine

The vaporization enthalpies and liquid vapor pressures from T = 298.15 K to T = 400 K of 1,3,5-triazine, pyrazine, pyrimidine, and pyridazine using pyridines and pyrazines as standards have been measured by correlation-gas chromatography. The vaporization enthalpies of 1,3,5-triazine (38.8 ± 1.9 kJ mol⁻¹) and pyrazine (40.5 ± 1.7 kJ mol⁻¹) obtained by these correlations are in good agreement with current literature values. The value obtained for pyrimidine (41.0 ± 1.9 kJ mol⁻¹) can be compared with a literature value of 50.0 kJ mol⁻¹. Combined with the condensed phase enthalpy of formation in the literature, this results in a gas-phase enthalpy of formation, Δ_f H _m (g, 298.15 K), of 187.6 ± 2.2 kJ mol⁻¹ for pyrimidine, compared to a value of 195.1 ± 2.1 calculated for pyrazine. Vapor pressures also obtained by correlation are used to predict boiling temperatures (BT). Good agreement with experimental BT (±4.2 K) including results for pyrimidine is observed for most compounds with the exception of the pyridazines. The results suggest that compounds containing one or two nitrogen atoms in the ring are suitable standards for correlating various heterocyclic compounds provided the nitrogen atoms are isolated from each other by carbon. Pyridazines do not appear to be evaluated correctly using pyridines and pyrazines as standards.     

Clay-vesicle interactions: fluorescence measurements and structural implications for slow release formulations of herbicides

Clay-vesicle systems exhibit a potential for environmental applications, such as herbicide formulations for reduced leaching. Clay-vesicle interactions were addressed by combining adsorption and XRD measurements with fluorescence studies for didodecyldimethylammonium bromide (DDAB), dioctadecyldimethylammonium bromide (DDOB), and montmorillonite. XRD and adsorption data indicated that the adsorbing vesicles were transformed after 3 days into paraffinic and bilayer structures. Fluorescence studies revealed that adsorption was almost complete within 5 min for a loading below the cation exchange capacity (CEC). Aggregation and sedimentation of clay-surfactant particles occurred within several minutes. Fluorescent measurements of supernatants indicated decomposition of vesicles at a high clay/surfactant ratio due to rapidly adsorbing cationic monomers. The kinetics of energy transfer between vesicles labeled by NBD-PE (1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-(7-nitro-2-1,3-benzoxadiazol-4-yl)) and montmorillonite labeled by rhodamine-B follows that of aggregation of surfactant-clay particles and structural changes of the vesicles at times of minutes to hours. Experiments following the reduction of NBD fluorescence by addition of dithionite indicate faster permeabilization of DDOB than DDAB vesicles, which was confirmed by leakage experiments. The faster permeabilization of DDOB vesicles in the presence of clay was correlated with their inferior suitability for the preparation of clay-based formulations of anionic herbicides for slow release.     

UV photochemical vapor generation-atomic fluorescence spectrometric determination of conventional hydride generation elements

A systematic investigation of UV photochemical vapor generation (photo-CVG) and its potential application for seven typical hydride-forming elements (As, Sb, Bi, Te, Sn, Pb and Cd) when combined with atomic fluorescence spectrometry (AFS) detection is presented. These analyte ions were converted to volatile species following UV irradiation of their aqueous solution to which low molecular weight organic acids (such as formic, acetic or propionic acid) had been added, and introduced to an atomic fluorescence spectrometer for subsequent analytical measurements. The experimental conditions for photo-CVG and the interferences arising from concomitant elements were carefully investigated. Limits of detection as low as 0.08, 0.1, 0.2 and 0.5 ng mL^− 1 were obtained for Te, Bi, Sb and As, respectively, comparable to those by hydride generation-AFS. The RSDs obtained with the proposed method for these elements were better than 5% at 50 ng mL^− 1. It is noteworthy that the presence of TiO₂ nanoparticles combined with UV irradiation remarkably enhances the CVG efficiencies of Se(VI) and Te(VI), which cannot form hydrides with KBH₄/NaBH₄. Moreover, photo-CVG has a greater tolerance toward interferences arising from transition elements than hydride generation, and this facilitates its application to the analysis of complicated sample matrices.