Structural Study of Polystyrene-b-poly(acrylic acid) Micelles Complexed with Uranyl: A SAXS Core-Shell Model Analysis.

The interactions between natural colloidal organic matter and actinides in solutions are complex and not fully understood. In this work, a crew-cut polystyrene-b-poly(acry1ic acid) (PS-b-PAA) micelle is proposed as a model particle for humic acid (HA) colloid with the aim to better understand the sequestration, aggregation, and mobility of HA colloids in the presence of uranyl ions. The effects of uranyl ions on the structure of PS29k-b-PAA5k micelles in aqueous solution were mainly investigated by synchrotron small-angle X-ray scattering. A core-shell model, accounting for the thickness and contrast changes of the PAA corona induced by the adsorption of uranyl, was employed to analyze the scattering data. A combination of transmission electron microscopy, dynamic light scattering, and zetametry showed a strong affinity of uranyl ions to PAA segments in water at pH 4-5 that resulted in the shrinkage and improved contrast of the PAA corona, as well as colloidal destabilization at a high uranyl concentration.

Redox-Responsive Colloidal Particles Based on Coordination Polymers Incorporating Viologen Units.

Colloidal particles based on supramolecular polymers are emerging as promising functional materials because of their intrinsic dynamic features and the possibility of stimuli responsivity. In this work, ≈200 nm self-assembled redox-responsive colloidal particles made of 1D-coordination polymers were readily prepared. In these metallopolymers, organic entities made of bis(viologen) groups covalently associated with terpyridine units are spontaneously bridged by Zn2+ cations through the formation of coordination bonds. The properties of these particles were analyzed and their redox activities investigated. Upon reduction of the viologen units, the formation of π-dimers between the reduced viologen moieties was demonstrated by spectroscopic experiments. It was shown that intermolecular π-dimers (i.e., between different polymer chains) that do not exist in homogeneous polymer solutions were, nevertheless, formed in the particle's structure because of the effects of confinement. The presence of these π-dimers allows stabilization of the charge in the colloids.

Auto-degradable and biocompatible superparamagnetic iron oxide nanoparticles/polypeptides colloidal polyion complexes with high density of magnetic material.

HYPOTHESIS: Superparamagnetic iron oxide nanoparticles (SPIONs) are extensively used as building block of colloidal nanocomposites for biomedical applications. Strategies employed to embed them in a biodegradable and biocompatible polymer matrix often fail to achieve a high density of loading which would greatly benefit to applications such as imaging and hyperthermia. In this study, poly(acrylic acid) coated SPION (γ-Fe2O3-PAA) are self-assembled with hydrolysable poly(serine ester) by electrostatic complexation, leading to perfectly defined spherical particles with ultra-high density of magnetic material and an ability to auto-degrade into individual SPION and biocompatible byproducts. EXPERIMENTS: Self-assembly and auto-degradation of γ-Fe2O3-PAA/poly(serine ester) and γ-Fe2O3-PAA/poly(serine ester)-b-PEG colloidal particles are studied by light scattering and microscopy. Colloidal stability in bio-fluids, hyperthermia under alternating magnetic field, cellular uptake, cytotoxicity and degradation of γ-Fe2O3-PAA/poly(serine ester)-b-PEG in living cells are investigated. FINDINGS: A remarkably slow electrostatic complexation leads to dense superparamagnetic γ-Fe2O3-PAA/poly(serine ester)-b-PEG polyion complexes (PICs) with controlled sizes (150-500 nm) and times of degradation in aqueous solvents (700-5000 h). The material shows good sustainability during hyperthermia, is well taken up by MC3T3 cells and non-cytotoxic. TEM images reveal a mechanism of degradation by "peeling" and fragmentation. In cells, PICs are reduced into individual SPIONs within 72 h.

Janus multi-responsive superparamagnetic nanoparticles functionalized with two on-demand and independently cleavable ligands for Actinide separation.

HYPOTHESIS: Nanoparticles functionalized with ligands which can on-demand and remotely be detached have recently attracted interest as stimuli-responsive materials. Research is now focused on multi-responsive systems, with applications in environmental science and biomedicine. The possibility to covalently couple two different ligands on a single nanoparticles, and to release them independently is investigated. This concept of nanoparticles functionalized with dual on-demand cleavable ligands is exploited in ground water decontamination and radionuclides separation. Efficient separation of contaminants in a single step is expected, simplifying partitioning process and decreasing generation of secondary waste by nuclear industry. EXPERIMENTS: Sub-10 nm Janus superparamagnetic nanoparticles are functionalized by click-chemistry (thiol and Diels-Alder) with two different Actinide-specific chelators. The reversible covalent bonds allow to detach chelators independently by either pH- or thermo-stimulation. The nanoparticles decorated with diethylenetriamine-pentaacetic acid (DTPA) and [(2-furan-2-yl-2-hydroxy-ethylcarbamoyl)-methoxy]-acetic acid (FHECMAA) are incubated with UO22+ and La3+ (as substitute for Pu3+) at pH = 3 and 7 before chelator-metal complexes are released. Metal contents are measured to determine separation efficiency. FINDINGS: Chelators can be detached from Janus nanoparticles with perfect selectivity. The nanoparticles are highly efficient for extraction of metals in acidic medium and show good ability for separation of U and La at neutral pH.

Heterostructured ZnFe2O4/Fe2TiO5/TiO2 Composite Nanotube Arrays with an Improved Photocatalysis Degradation Efficiency Under Simulated Sunlight Irradiation.

To improve the visible light absorption and photocatalytic activity of titanium dioxide nanotube arrays (TONTAs), ZnFe2O4 (ZFO) nanocrystals were perfused into pristine TONTA pipelines using a novel bias voltage-assisted perfusion method. ZFO nanocrystals were well anchored on the inner walls of the pristine TONTAs when the ZFO suspensions (0.025 mg mL-1) were kept under a 60 V bias voltage for 1 h. After annealing at 750 °C for 2 h, the heterostructured ZFO/Fe2TiO5 (FTO)/TiO2 composite nanotube arrays were successfully obtained. Furthermore, Fe3+ was reduced to Fe2+ when solid solution reactions occurred at the interface of ZFO and the pristine TONTAs. Introducing ZFO significantly enhanced the visible light absorption of the ZFO/FTO/TONTAs relative to that of the annealed TONTAs. The coexistence of type I and staggered type II band alignment in the ZFO/FTO/TONTAs facilitated the separation of photogenerated electrons and holes, thereby improving the efficiency of the ZFO/FTO/TONTAs for photocatalytic degradation of methylene blue when irradiated with simulated sunlight.

A New First Break Picking for Three-Component VSP Data Using Gesture Sensor and Polarization Analysis.

A new first break picking for three-component (3C) vertical seismic profiling (VSP) data is proposed to improve the estimation accuracy of first arrivals, which adopts gesture detection calibration and polarization analysis based on the eigenvalue of the covariance matrix. This study aims at addressing the problem that calibration is required for VSP data using the azimuth and dip angle of geophones, due to the direction of geophones being random when applied in a borehole, which will further lead to the first break picking possibly being unreliable. Initially, a gesture-measuring module is integrated in the seismometer to rapidly obtain high-precision gesture data (including azimuth and dip angle information). Using re-rotating and re-projecting using earlier gesture data, the seismic dataset of each component will be calibrated to the direction that is consistent with the vibrator shot orientation. It will promote the reliability of the original data when making each component waveform calibrated to the same virtual reference component, and the corresponding first break will also be properly adjusted. After achieving 3C data calibration, an automatic first break picking algorithm based on the autoregressive-Akaike information criterion (AR-AIC) is adopted to evaluate the first break. Furthermore, in order to enhance the accuracy of the first break picking, the polarization attributes of 3C VSP recordings is applied to constrain the scanning segment of AR-AIC picker, which uses the maximum eigenvalue calculation of the covariance matrix. The contrast results between pre-calibration and post-calibration using field data show that it can further improve the quality of the 3C VSP waveform, which is favorable to subsequent picking. Compared to the obtained short-term average to long-term average (STA/LTA) and the AR-AIC algorithm, the proposed method, combined with polarization analysis, can significantly reduce the picking error. Applications of actual field experiments have also confirmed that the proposed method may be more suitable for the first break picking of 3C VSP. Test using synthesized 3C seismic data with low SNR indicates that the first break is picked with an error between 0.75 ms and 1.5 ms. Accordingly, the proposed method can reduce the picking error for 3C VSP data.

DOUBLE-EXPONENTIAL FITTING FUNCTION FOR EVALUATION OF COSMIC-RAY-INDUCED NEUTRON FLUENCE RATE IN ARBITRARY LOCATIONS.

The fluence rate of cosmic-ray-induced neutrons (CRINs) varies with many environmental factors. While many current simulation and experimental studies have focused mainly on the altitude variation, the specific rule that the CRINs vary with geomagnetic cutoff rigidity (which is related to latitude and longitude) was not well considered. In this article, a double-exponential fitting function F=(A1e-A2CR+A3)eB1Al, is proposed to evaluate the CRINs' fluence rate varying with geomagnetic cutoff rigidity and altitude. The fitting R2 can have a value up to 0.9954, and, moreover, the CRINs' fluence rate in an arbitrary location (latitude, longitude and altitude) can be easily evaluated by the proposed function. The field measurements of the CRINs' fluence rate and H*(10) rate in Mt. Emei and Mt. Bowa were carried out using a FHT-762 and LB 6411 neutron prober, respectively, and the evaluation results show that the fitting function agrees well with the measurement results.

High-speed multi-THz-range mode-hop-free tunable mid-IR laser spectrometer.

We report on a widely (2.25 THz or 75 cm(-1)) and rapidly (4.5 THz/s) mode-hop-free (MHF) tunable mid-IR laser source at ~3.3 µm, consisting of a 5%-MgO:LiNbO(3) singly resonant optical parametric oscillator (SRO) pumped by an automated broadly MHF tunable extended-cavity diode laser (ECDL). The broad and rapid MHF tuning capability of the ECDL is readily transferred to the SRO idler wave owing to the quasi-noncritical pump spectral acceptance bandwidth of the quasi-phase-matching. Fast and broadband high-resolution Doppler spectroscopy measurements of the ν(3) band of CH(4) are presented to illustrate the performance of the mid-IR optical parametric oscillator spectrometer.

Coupled-cavity ring-down spectroscopy technique.

We present a technique called coupled-cavity ring-down spectroscopy (CC-RDS) for controlling the finesse of an optical resonator. Applications include extending the sensitivity and dynamic range of a cavity-enhanced spectrometer as well as widening the useful spectral region of high-reflectivity mirrors. CC-RDS uses controlled feedback of the probe laser beam to a ring-down cavity, which leads to interference between the internally circulating light and that which is fed back through a cavity mirror port. Using a 74 cm long ring-down cavity and a feedback cavity with a finesse of 16, we demonstrate that this effect increases the decay time constant from 210 µs to 280 µs, corresponding to an increase of finesse from 2.7×10(5) to 3.6×10(5). Finally, we show that with the addition of a second feedback cavity, we observe ring-down times as long as ~0.5 ms, which is equivalent to (1-R)≈4.9×10(-6), where R is the effective mirror reflectivity.

High-speed off-axis Cavity Ring-Down Spectroscopy with a re-entrant configuration for spectral resolution enhancement.

Monitoring of changing samples by Cavity Ring-Down Spectroscopy (CRDS) is possible using fast frequency scans of the laser and/or the cavity resonance. Mode-matched cavity excitation improves performance of fast CRDS but data-points result separated by the cavity Free Spectral Range (FSR): low pressure samples demand long cavities. We demonstrate fast CRDS with off-axis injection of a "re-entrant" resonator yielding FSR/N data-points separation. Our N = 4 short-cavity setup is found to perform well compared with other fast-CRDS implementations. Interestingly, the intrinsic chirped ringing affecting ring-down signals in mode-matched fast-CRDS disappear with off-axis injection. This is due to a fine splitting of the re-entrant-cavity degenerate groups of modes by astigmatism.