Solvation structure and dynamics of coumarin 153 in an imidazolium-based ionic liquid with chloroform, benzene, and propylene carbonate.

In order to determine the self-diffusion coefficients D of all the species in the solutions at 298.2 K, 1H and 19F NMR diffusion ordered spectroscopy (DOSY) has been conducted on coumarin 153 (C153) in binary mixed solvents of an imidazolium-based ionic liquid (IL), 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (C12mimTFSA), with three molecular liquids (MLs) of chloroform (CL), benzene (BZ), and propylene carbonate (PC) as a function of ML mole fraction xML. Below xML ≈ 0.8, the D values of each species do not significantly depend on the MLs. However, above this mole fraction, the diffusion of C153 becomes smoother in the order of BZ ≈ CL > PC systems. The interactions among C153, C12mim+, TFSA-, and ML molecules have been investigated using infrared (IR) and 1H and 13C NMR spectroscopic techniques. The relations of the diffusion of the species with the interactions among them have been discussed on the molecular scale. In the IL solution, the C153 carbonyl oxygen atom is hydrogen-bonded with the imidazolium ring C2-H atom of C12mim+. C12mim+ also forms an ion pair with TFSA-. Thus, C153, C12mim+, and TFSA- cooperatively move in the CL and BZ solutions at a lower ML content, xML < ∼0.8. On the other hand, at a higher ML content, xML > ∼0.8, the C153 molecule diffuses with CL and BZ molecules because of the hydrogen bonding between the C153 carbonyl O atom and the CL H atom and the π-π interaction between the C153 and BZ ring planes, respectively. For the PC system, the change in the relative self-diffusion coefficients of each species with increasing xML differs from those for the CL and BZ systems because of both hydrogen bonding donor H and acceptor O atoms of PC for C153, the IL cation and anion, and PC themselves.

Caged-Sphere Optofluidic Sensors: Whispering Gallery Resonators in Wicking Microfluidics.

The rapid development of optofluidic technologies in recent years has seen the need for sensing platforms with ease-of-use, simple sample manipulation, and high performance and sensitivity. Herein, an integrated optofluidic sensor consisting of a pillar array-based open microfluidic chip and caged dye-doped whispering gallery mode microspheres is demonstrated and shown to have potential for simple real-time monitoring of liquids. The open microfluidic chip allows for the wicking of a thin film of liquid across an open surface with subsequent evaporation-driven flow enabling continuous passive flow for sampling. The active dye-doped whispering gallery mode microspheres placed between pillars, avoid the use of cumbersome fibre tapers to couple light to the resonators as is required for passive microspheres. The performance of this integrated sensor is demonstrated using glucose solutions (0.05-0.3 g/mL) and the sensor response is shown to be dynamic and reversible. The sensor achieves a refractive index sensitivity of ~40 nm/RIU, with Q-factors of ~5 × 103 indicating a detection limit of ~3 × 10-3 RIU (~20 mg/mL glucose). Further enhancement of the detection limit is expected by increasing the microsphere Q-factor using high-index materials for the resonators, or alternatively, inducing lasing. The integrated sensors are expected to have significant potential for a host of downstream applications, particularly relating to point-of-care diagnostics.

A Picosecond Time-Resolved Spectroscopic Investigation of the Effect of pH on Morin Fluorescence.

In this work, we investigated for the first time morin in MeOH at different pH values by picosecond time-resolved fluorescence. We identified the two species responsible for the fluorescence at low and high pH. The solvated morin-solvent hydrogen-bonded complex has been experimentally observed for the first time. We give also the typical fluorescence spectra as well as the fluorescence lifetimes of the probable emitting species. In this work we put forward new insights concerning the contribution of free morin to the fluorescence. We hope that these new data improve the accuracy of the interpretation of the cation:morin complexes titration using fluorescence signal.

Dynamics in the BMIM PF6/acetonitrile mixtures observed by femtosecond optical Kerr effect and molecular dynamics simulations.

We have performed the measurements of the optical Kerr effect signal time evolution up to 4 ns for a mixture of 1-alkyl-3-methyl-imidazolium hexafluorophosphate (BMIM PF6) ionic liquid and acetonitrile in the whole mole fractions range. The long delay line in our experimental setup allowed us to capture the complete reorientational dynamics of the ionic liquid. We have analysed the optical Kerr effect signal in the time and frequency domains with help of molecular dynamics simulations. In our approximation of the slow picosecond dynamics with a multi-exponential decay, we distinguish three relaxation times. The highest two are assigned to the reorientation of the cation and acetonitrile molecules that are in the vicinity of the imidazolium ring. The third one is recognized as originating from cation rotations and reorientation of acetonitrile molecules in the bulk or in the vicinity of the aliphatic chains of the cation. With help of the simulation we interpret the intermolecular band in the reduced spectral density, obtained from Kerr signal, as follows: its low-frequency side results from oscillations of one of the components in the cage formed by its neighbors, while the high-frequency side is attributed to the librations of the cation and acetonitrile molecule as well as the intermolecular oscillations of system components involved in specific interactions. We use this assignment and concentration dependence of the spectra obtained from velocity and angular velocity correlations to explain the mole fraction dependence of Kerr reduced spectral density.

Personalized 177Lu-octreotate peptide receptor radionuclide therapy of neuroendocrine tumours: initial results from the P-PRRT trial.

PURPOSE: Peptide receptor radionuclide therapy (PRRT) is mostly administered using a fixed injected activity (IA) per cycle. This empiric regime results in highly variable absorbed doses to the critical organs and undertreatment of the majority of patients. We conceived a personalized PRRT protocol in which the IA is adjusted to deliver a prescribed absorbed dose to the kidney, with the aim to safely increase tumour irradiation. We herein report on the initial results of our prospective study of personalized PRRT, the P-PRRT Trial (NCT02754297). METHODS: PRRT-naïve patients with progressive and/or symptomatic neuroendocrine tumour (NET) were scheduled to receive a four-cycle induction course of 177Lu-octreotate with quantitative SPECT/CT-based dosimetry. The IA was personalized according to the glomerular filtration rate and the body surface area for the first cycle, and according to the prior renal Gy/GBq for the subsequent cycles. The prescribed renal absorbed dose of 23 Gy was reduced by 25-50% in case of significant renal or haematological impairment. Responders were allowed to receive consolidation or maintenance cycles, for each of which 6 Gy to the kidney were prescribed. We simulated the empiric PRRT regime by fixing the IA at 7.4 GBq per cycle, with the same percentage reductions as above. Radiological, molecular imaging, biochemical, and quality of life responses, as well as safety, were assessed. RESULTS: Fifty-two patients underwent 171 cycles. In 34 patients who completed the induction course, a median cumulative IA of 36.1 (range, 6.3-78.6) GBq was administered, and the median cumulative kidney and maximum tumour absorbed doses were 22.1 (range, 8.3-24.3) Gy and 185.7 (range: 15.2-443.1) Gy respectively. Compared with the simulated fixed-IA induction regime, there was a median 1.26-fold increase (range, 0.47-2.12 fold) in the cumulative maximum tumour absorbed dose, which was higher in 85.3% of patients. In 39 assessable patients, the best objective response was partial response in nine (23.1%), minor response in 14 (35.9%), stable disease in 13 (33.3%) and progressive disease in three patients (7.7%). In particular, 11 of 13 patients (84.6%) with pancreatic NET had partial or minor response. The global health status/quality of life score significantly increased in 50% of patients. Acute and subacute side-effects were all of grade 1 or 2, and the most common were nausea (in 32.7% of patients) and fatigue (in 30.8% of patients) respectively. Subacute grade 3 or 4 toxicities occurred in less than 10% of patients, with the exception of lymphocytopenia in 51.9% of patients, without any clinical consequences however. No patient experienced severe renal toxicity. CONCLUSIONS: Personalized PRRT makes it possible to safely increase tumour irradiation in the majority of patients. Our first results indicate a favourable tolerance profile, which appears similar to that of the empiric regime. The response rates are promising, in particular in patients with NET of pancreatic origin.

The local structure in the BmimPF6/acetonitrile mixture: the charge distribution effect.

The changes of the local structure in the binary mixture of 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6) ionic liquid and acetonitrile are investigated over the entire composition range. Two charge distribution models of the ions are considered: in the first one, the atomic fractional charges of the cations and anions are kept equal with those in the neat ionic liquid, and hence they are independent from the mole fraction of the ionic liquid, while in the second one the charge distribution is scaled up by a mole fraction dependent factor. The sum of these charges converge to +1e and -1e on the cation and anion, respectively, at infinite dilution. All the other interactions and geometry parameters of the ions (i.e., Lennard-Jones, bond stretching, angle bending and dihedral parameters) are identical in the two cases. The effect of the fractional charge distribution on the hydrogen bonding between the counterions themselves and between the ions and solvent molecules, as well as on the stacking interactions between the cations, is analyzed. To this end, two distances, characteristic of the hydrogen bond formed by the donor moiety and its nearest neighbor acceptor, as well as a coordinate system that defines unambiguously the orientation between a reference cation and its nearest neighbor, are introduced. It is shown that, with the variable charge model, the neighboring cation-anion pairs maintain their relative arrangement similar to the neat ionic liquid down to an ionic liquid mole fraction of xIL = 0.10, whereas in the case of the constant charge model such changes occur already at xIL = 0.20. Furthermore, the analysis of the first and the second nearest neighbor distance distributions of an anion around a reference cation indicates that, at this mole fraction range, there are two different preferred arrangements of the anions around the cations. In the first one, similarly to the local structure around a reference cation in the neat ionic liquid, the anion forms a distorted hydrogen bond with the cation, while in the second one the anion is located farther from the cation, forming no hydrogen bond with it. The relative population of these two types of preferred nearest neighbor cation-anion arrangements is found to be sensitive to further decrease of the ionic liquid mole fraction. These findings correlate with experimental results concerning the behavior of many physical chemical properties (e.g., excess volume, excess viscosity, chemical shift, infrared and Raman vibrational mode shifts, diffusion, etc.) that were found to undergo a drastic change in this mole fraction range. Our results show that in this composition range a transition occurs from the situation where the macroscopic physical chemical properties of the system are determined primarily by the cation-anion hydrogen bonding interactions to that where they are determined by the solvation of the cation and the anion by the molecular solvent.

Endohedral gallide cluster superconductors and superconductivity in ReGa5.

We present transition metal-embedded (T@Gan) endohedral Ga-clusters as a favorable structural motif for superconductivity and develop empirical, molecule-based, electron counting rules that govern the hierarchical architectures that the clusters assume in binary phases. Among the binary T@Gan endohedral cluster systems, Mo8Ga41, Mo6Ga31, Rh2Ga9, and Ir2Ga9 are all previously known superconductors. The well-known exotic superconductor PuCoGa5 and related phases are also members of this endohedral gallide cluster family. We show that electron-deficient compounds like Mo8Ga41 prefer architectures with vertex-sharing gallium clusters, whereas electron-rich compounds, like PdGa5, prefer edge-sharing cluster architectures. The superconducting transition temperatures are highest for the electron-poor, corner-sharing architectures. Based on this analysis, the previously unknown endohedral cluster compound ReGa5 is postulated to exist at an intermediate electron count and a mix of corner sharing and edge sharing cluster architectures. The empirical prediction is shown to be correct and leads to the discovery of superconductivity in ReGa5. The Fermi levels for endohedral gallide cluster compounds are located in deep pseudogaps in the electronic densities of states, an important factor in determining their chemical stability, while at the same time limiting their superconducting transition temperatures.

Mode-Splitting for Refractive Index Sensing in Fluorescent Whispering Gallery Mode Microspheres with Broken Symmetry.

Whispering gallery mode (WGM) resonators have become increasingly diverse in terms of both architecture and applications, especially as refractometric sensors, allowing for unprecedented levels of sensitivity. However, like every refractometric sensor, a single WGM resonator cannot distinguish temperature variations from changes in the refractive index of the surrounding environment. Here, we investigate how breaking the symmetry of an otherwise perfect fluorescent microsphere, by covering half of the resonator with a high-refractive-index (RI) glue, might enable discrimination of changes in temperature from variations in the surrounding refractive index. This novel approach takes advantage of the difference of optical pathway experienced by WGMs circulating in different equatorial planes of a single microsphere resonator, which induces mode-splitting. We investigated the influence of the surrounding RI of the microsphere on mode-splitting through an evaluation of the sphere's WGM spectrum and quality factor (Q-factor). Our results reveal that the magnitude of the mode-splitting increases as the refractive index contrast between the high-refractive-index (RI) glue and the surrounding environment increases, and that when they are equal no mode-splitting can be seen. Investigating the refractive index sensitivity of the individual sub modes resulting from the mode-splitting unveils a new methodology for RI sensing, and enables discrimination between surrounding refractive index changes and temperature changes, although it comes at the cost of an overall reduced refractive index sensitivity.

Two-Dimensional Layered Nanomaterial-Based One-Dimensional Photonic Crystal Refractive Index Sensor.

One-dimensional photonic crystal (1DPC) sensors have emerged as contenders for traditional surface plasmon resonance sensors, owing to their potential for the detection of bigger molecules and particles due to their higher interaction volume in the sensing medium. Two-dimensional layered nanomaterials, most notably graphene and dichalcogenides (e.g., MoS2, MoSe2, WS2, and WSe2), have shown higher refractive index sensitivity because of their absorption as well as adsorption property. The proposed configuration of 1DPC presented consists of alternate layers of the aforementioned nanomaterials and silicon. The performance parameters, namely the sensitivity, resolution, quality factor, and the evanescent field penetration depth, are calculated and compared with 1DPC having poly methyl methacrylate (PMMA) in place of silicon. Increased shift in resonance angle and quality factor are observed by replacing PMMA with silicon, but at the cost of decreased resolution. Further, our results show that although the sensitivity and quality factor of the 1DPC sensor is less than that of the conventional surface plasmon resonance sensor (SPR) with a gold thin film, it has much higher resolution and penetration depth to make it suitable for large molecules.

Personalized 177Lu-octreotate peptide receptor radionuclide therapy of neuroendocrine tumours: a simulation study.

PURPOSE: Peptide receptor radionuclide therapy (PRRT) with 177Lu-octreotate is commonly administered at empiric, fixed amounts of injected radioactivity (IA). This results in highly variable absorbed doses to critical organs and suboptimal treatment of most patients. The primary aims of this study were to design a personalized PRRT (P-PRRT) protocol based on dosimetry, and to perform a simulation of this protocol in a retrospective cohort of patients with neuroendocrine tumours, in order to assess the potential of P-PRRT to safely increase the absorbed dose to the tumour during a four-cycle induction course. METHODS: Thirty-six patients underwent 122 fixed-IA 177Lu-octreotate PRRT cycles with quantitative SPECT/CT-based dosimetry. Twenty-two patients completed a four-cycle induction course (29.6 ± 2.4 GBq cumulative IA), with kidney, bone marrow and maximum tumour absorbed doses of 16.2 ± 5.5, 1.3 ± 0.8, and 114 ± 66 Gy, respectively. We simulated a P-PRRT regime in which the renal absorbed dose per IA was predicted by the body surface area and glomerular filtration rate for the first cycle, and by renal dosimetry of the previous cycle(s) for the following cycles. Personalized IA was adjusted at each cycle in order to reach the prescribed renal absorbed dose of 23 Gy over four cycles (with a 25-50% reduction when renal or bone marrow function was impaired). Simulated IA and absorbed doses were based on actual patient characteristics, laboratory values and absorbed doses per IA delivered at each cycle. RESULTS: In the P-PRRT regime, cumulative IA could have been increased to 43.7 ± 16.5 GBq over four induction cycles (10.9 ± 5.0 GBq per cycle), yielding cumulative kidney, bone marrow and maximum tumour absorbed doses of 21.5 ± 2.5, 1.63 ± 0.61, and 163.4 ± 85.9 Gy, respectively. This resulted in an average 1.48-fold increase in cumulative maximum tumour absorbed dose over empiric PRRT (range, 0.68-2.64-fold; P = 0.0013). CONCLUSION: By standardizing the renal absorbed dose delivered during the induction course, P-PRRT has the potential to significantly increase tumour absorbed dose, thus to augment the therapeutic benefit while limiting toxicity.

Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations.

The information about the structure of dimethyl sulfoxide (DMSO)-water mixtures at relatively low DMSO mole fractions is an important step in order to understand their cryoprotective properties as well as the solvation process of proteins and amino acids. Classical MD simulations, using the potential model combination that best reproduces the free energy of mixing of these compounds, are used to analyze the local structure of DMSO-water mixtures at DMSO mole fractions below 0.2. Significant changes in the local structure of DMSO are observed around the DMSO mole fraction of 0.1. The array of evidence, based on the cluster and the metric and topological parameters of the Voronoi polyhedra distributions, indicates that these changes are associated with the simultaneous increase of the number of DMSO-water and decrease of water-water hydrogen bonds with increasing DMSO concentration. The inversion between the dominance of these two types of H-bonds occurs around XDMSO = 0.1, above which the DMSO-DMSO interactions also start playing an important role. In other words, below the DMSO mole fraction of 0.1, DMSO molecules are mainly solvated by water molecules, while above it, their solvation shell consists of a mixture of water and DMSO. The trigonal, tetrahedral, and trigonal bipyramidal distributions of water shift to lower corresponding order parameter values indicating the loosening of these orientations. Adding DMSO does not affect the hydrogen bonding between a reference water molecule and its first neighbor hydrogen bonded water molecules, while it increases the bent hydrogen bond geometry involving the second ones. The close-packed local structure of the third, fourth, and fifth water neighbors also is reinforced. In accordance with previous theoretical and experimental data, the hydrogen bonding between water and the first, the second, and the third DMSO neighbors is stronger than that with its corresponding water neighbors. At a given DMSO mole fraction, the behavior of the intensity of the high orientational order parameter values indicates that water molecules are more ordered in the vicinity of the hydrophilic group while their structure is close-packed near the hydrophobic group of DMSO.

Dynamic Self-Referencing Approach to Whispering Gallery Mode Biosensing and Its Application to Measurement within Undiluted Serum.

Biosensing within complex biological samples requires a sensor that can compensate for fluctuations in the signal due to changing environmental conditions and nonspecific binding events. To achieve this, we developed a novel self-referenced biosensor consisting of two almost identically sized dye-doped polystyrene microspheres placed on adjacent holes at the tip of a microstructured optical fiber (MOF). Here self-referenced biosensing is demonstrated with the detection of Neutravidin in undiluted, immunoglobulin-deprived human serum samples. The MOF allows remote excitation and collection of the whispering gallery modes (WGMs) of the microspheres while also providing a robust and easy to manipulate dip-sensing platform. By taking advantage of surface functionalization techniques, one microsphere acts as a dynamic reference, compensating for nonspecific binding events and changes in the environment (such as refractive index and temperature), while the other microsphere is functionalized to detect a specific interaction. The almost identical size allows the two spheres to have virtually identical refractive index sensitivity and surface area, while still having discernible WGM spectra. This ensures their responses to nonspecific binding and environmental changes are almost identical, whereby any specific changes, such as binding events, can be monitored via the relative movement between the two sets of WGM peaks.

Lasing of whispering gallery modes in optofluidic microcapillaries.

This paper demonstrates lasing of the whispering gallery modes in polymer coated optofluidic capillaries and their application to refractive index sensing. The laser gain medium used here is fluorescent Nile Red dye, which is embedded inside the high refractive index polymer coating. We investigate the refractometric sensing properties of these devices for different coating thicknesses, revealing that the high Q factors required to achieve low lasing thresholds can only be realized for relatively thick polymer coatings (in this case ≥ 800 nm). Lasing capillaries therefore tend to have a lower refractive index sensitivity, compared to non-lasing capillaries which can have a thinner polymer coating, due to the stronger WGM confinement within the polymer layer. However we find that the large improvement in signal-to-noise ratio realized for lasing capillaries more than compensates for the decreased sensitivity and results in an order-of-magnitude improvement in the detection limit for refractive index sensing.

Refractometric micro-sensor using a mirrored capillary resonator.

We report on a flow-through optical sensor consisting of a microcapillary with mirrored channels. Illuminating the structure from the side results in a complicated spectral interference pattern due to the different cavities formed between the inner and outer capillary walls. Using a Fourier transform technique to isolate the desired channel modes and measure their resonance shift, we obtain a refractometric detection limit of (6.3 ± 1.1) x 10-6 RIU near a center wavelength of 600 nm. This simple device demonstrates experimental refractometric sensitivities up to (5.6 ± 0.2) x 102 nm/RIU in the visible spectrum, and it is calculated to reach 1540 nm/RIU with a detection limit of 2.3 x 10-6 RIU at a wavelength of 1.55 µm. These values are comparable to or exceed some of the best Fabry-Perot sensors reported to date. Furthermore, the device can function as a gas or liquid sensor or even as a pressure sensor owing to its high refractometric sensitivity and simple operation.

Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far-Red (Polarized) Luminescence.

The physicochemical properties of cationic dioxa (1), azaoxa (2), and diaza (3) [6]helicenes demonstrate a much higher chemical stability of the diaza adduct 3 (pKR+ =20.4, Ered1/2 =-0.72 V) compared to its azaoxa 2 (pKR+ =15.2, Ered1/2 =-0.45 V) and dioxa 1 (pKR+ =8.8, Ered1/2 =-0.12 V) analogues. The fluorescence of these cationic chromophores is established, and ranges from the orange to the far-red regions. From 1 to 3, a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31 % and 9.8 ns, respectively, at 658 nm) are observed. The triplet quantum yields and circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6]helicene core is achieved through selective and orthogonal post-functionalization reactions (12 examples, compounds 4-15). The electronic absorption is modulated from the orange to the far-red spectral range (560-731 nm), and fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70 % (619 nm). The influence of the peripheral auxochrome substituents is rationalized by first-principles calculations.

Plasmonic Fiber Optic Refractometric Sensors: From Conventional Architectures to Recent Design Trends.

Surface Plasmon Resonance (SPR) fiber sensor research has grown since the first demonstration over 20 year ago into a rich and diverse field with a wide range of optical fiber architectures, plasmonic coatings, and excitation and interrogation methods. Yet, the large diversity of SPR fiber sensor designs has made it difficult to understand the advantages of each approach. Here, we review SPR fiber sensor architectures, covering the latest developments from optical fiber geometries to plasmonic coatings. By developing a systematic approach to fiber-based SPR designs, we identify and discuss future research opportunities based on a performance comparison of the different approaches for sensing applications.

Material candidates for optical frequency comb generation in microspheres.

This paper evaluates the opportunities for using materials other than silica for optical frequency comb generation in whispering gallery mode microsphere resonators. Different materials are shown to satisfy the requirement of dispersion compensation in interesting spectral regions such as the visible or mid-infrared and for smaller microspheres. This paper also analyses the prospects of comb generation in microspheres within aqueous solution for potential use in applications such as biosensing. It is predicted that to achieve comb generation with microspheres in aqueous solution the visible low-loss wavelength window of water needs to be exploited. This is because efficient comb generation necessitates ultra-high Q-factors, which are only possible for cavities with low absorption of the evanescent field outside the cavity. This paper explores the figure of merit for nonlinear interaction efficiency and the potential for dispersion compensation at unique wavelengths for a host of microsphere materials and dimensions and in different surroundings.

Q-factor limits for far-field detection of whispering gallery modes in active microspheres.

This paper investigates the Q-factor limits imposed on the far-field detection of the whispering gallery modes of active microspherical resonators. It is shown that the Q-factor measured for a given active microsphere in the far-field using a microscope is significantly lower than that measured using evanescent field collection through a taper. The discrepancy is attributed to the inevitable small asphericity of microspheres that results in mode-splitting which becomes unresolvable in the far-field. Analytic expressions quantifying the Q-factor limits due to small levels of asphericity are subsequently derived.

Method for predicting whispering gallery mode spectra of spherical microresonators.

A full three-dimensional Finite-Difference Time-Domain (FDTD)-based toolkit is developed to simulate the whispering gallery modes of a microsphere in the vicinity of a dipole source. This provides a guide for experiments that rely on efficient coupling to the modes of microspheres. The resultant spectra are compared to those of analytic models used in the field. In contrast to the analytic models, the FDTD method is able to collect flux from a variety of possible collection regions, such as a disk-shaped region. The customizability of the technique allows one to consider a variety of mode excitation scenarios, which are particularly useful for investigating novel properties of optical resonators, and are valuable in assessing the viability of a resonator for biosensing.

Photoreduction of Sm(3+) in Nanocrystalline BaFCl.

We demonstrate that exposure of nanocrystalline BaFCl:Sm(3+) X-ray storage phosphor to blue laser pulses with peak power densities on the order of 10 GW/cm(2) results in conversion of Sm(3+) to Sm(2+). This photoreduction is found to be strongly power-dependent with an initial fast rate, followed by a slower rate. The photoreduction appears to be orders of magnitude more efficient than that for previously reported systems, and it is estimated that up to 50% of the samarium ions can be photoreduced to the divalent state. The main mechanism is most likely based on multiphoton electron-hole creation, followed by subsequent trapping of the electrons in the conduction band at the Sm(3+) centers. Nanocrystalline BaFCl:Sm(3+) is an efficient photoluminescent X-ray storage phosphor with possible applications as dosimetry probes, and the present study shows for the first time that the power levels of the blue light have to be kept relatively low to avoid the generation of Sm(2+) in the readout process. A system comprising the BaFCl:Sm(3+) nanocrystallites embedded into a glass is also envisioned for 3D memory applications.