Establishment of an immunofiltration strip for the detection of 17ß-estradiol based on the photothermal effect of black phosphorescence.

Recently, the photothermal effect of nanomaterials has opened the door for new appealing strategy, which can generate a promising and powerful tool when combined with immunoassay. As a new kind of nanomaterial, black phosphorus (BP) has aroused widespread interest. In this study, a novel immunofiltration strip method with temperature as the readout signal based on the photothermal effect of BP nanosheets was established. The temperature was monitored by a portable temperature sensor. Using an indirect competitive strategy, it provides a simple, rapid, sensitive, and economic platform for the detection of 17ß-estradiol, a kind of endocrine disrupting compound that is frequently detected in environmental water or food samples. The higher the concentration of 17ß-estradiol in the sample, the less BP nanosheets are brought to bind to the strip surface, along with lower temperature variation when exposed to intensive laser irradiation. Under optimum conditions, a detection limit of 0.104 ng mL-1 was achieved. The feasibility of this assay was assessed by a standard addition method in water and milk samples, showing good performance and indicating potential application value for easy-to-use, inexpensive, and on-site monitoring of 17ß-estradiol.

Phosphorus-doped TiO2 catalysts with stable anatase-brookite biphase structure: synthesis and photocatalytic performance.

Phosphorus-doped (P-doped) TiO2 catalysts with a stable anatase-brookite biphase structure were successfully synthesized by integrating ultrasonication with phosphorus doping and Pluronic P123 surfactant. The synthesized catalysts were characterized using X-ray diffraction, transmission electron microscopy, nitrogen adsorption-desorption, Fourier transform infrared, and UV-visible diffuse reflectance spectra. Ultrasonication facilitates the appearance of brookite phase. Phosphorus doping was demonstrated an effective strategy to stabilize the anatase-brookite biphase structure and inhibits undesirable grain growth. Triblock copolymer Pluronic P123 used in the reaction facilitates the formation of catalyst particles with mesoporous structure and large surface area and prevents particles from agglomeration. The low band-gap of brookite phase enables the synthesized P-doped TiO2 catalysts outperform commercial P25 TiO2 and N-doped TiO2 in the degradation of methylene blue under both solar light and visible light irradiation.

PLGA-collagen-BPNS Bifunctional composite mesh for photothermal therapy of melanoma and skin tissue engineering.

The treatment of melanoma requires not only the elimination of skin cancer cells but also skin regeneration to heal defects. To achieve this goal, a bifunctional composite scaffold of poly(DL-lactic-co-glycolic acid) (PLGA), collagen and black phosphorus nanosheets (BPNSs) was prepared by hybridizing a BPNS-embedded collagen sponge with a PLGA knitted mesh. The composite mesh increased the temperature under near-infrared laser irradiation. The incorporation of BPNSs provided the PLGA-collagen-BPNS composite mesh with excellent photothermal properties for the photothermal ablation of melanoma cells both in vitro and in vivo. The PLGA-collagen-BPNS composite mesh had high mechanical strength for easy handling. The PLGA-collagen-BPNS composite mesh facilitated the proliferation of fibroblasts, promoted the expression of angiogenesis-related genes and the genes of components of the extracellular matrix for skin tissue regeneration. The high mechanical strength, photothermal ablation capability and skin tissue regeneration effects demonstrate that the bifunctional PLGA-collagen-BPNS composite mesh is a versatile and effective platform for the treatment of melanoma and the regeneration of skin defects.

Bound exciton photoluminescence from ion­implanted phosphorus in thin silicon layers.

We report the observation of clear bound exciton (BE) emission from ion-implanted phosphorus. Shallow implantation and high-temperature annealing successfully introduce active donors into thin silicon layers. The BE emission at a wavelength of 1079 nm shows that a part of the implanted donors are definitely activated and isolated from each other. However, photoluminescence and electron spin resonance studies find a cluster state of the activated donors. The BE emission is suppressed by this cluster state rather than the nonradiative processes caused by ion implantation. Our results provide important information about ion implantation for doping quantum devices with phosphorus quantum bits.

Black Phosphorus Nanosheet Encapsulated by Zeolitic Imidazole Framework-8 for Tumor Multimodal Treatments.

Black phosphorus (BP) nanosheet is easily oxidized by oxygen and water under ambient environment, thus, reliable BP passivation techniques for biomedical applications is urgently needed. A simple and applicable passivation strategy for biomedical applications was established by encapsulating BP nanosheet into zeolitic imidazole framework-8 (ZIF-8). The resulted BP nanosheet in ZIF-8 (BP@ZIF-8) shows not only satisfied chemical stability in both water and phosphate buffered saline (PBS), but also excellent biocompatibility. Notably, BP nanosheet endows the prepared BP@ZIF-8 with prominent photothermal conversion efficiency (31.90%). Besides passivation BP, ZIF-8 provides the BP@ZIF-8 with high drug loading amount (1353.3 mg g-1). Moreover, the loaded drug can be controlled release by pH stimuli. Both in vitro and in vivo researches verified the resulted BP@ZIF-8 an ideal candidate for tumor multimodal treatments.

Novel Engineered Bacterium/Black Phosphorus Quantum Dot Hybrid System for Hypoxic Tumor Targeting and Efficient Photodynamic Therapy.

Intratumoral hypoxia significantly constrains the susceptibility of solid tumors to oxygen-dependent photodynamic therapy (PDT), and effort to reverse such hypoxia has achieved limited success to date. Herein, we developed a novel engineered bacterial system capable of targeting hypoxic tumor tissues and efficiently mediating the photodynamic treatment of these tumors. For this system, we genetically engineered Escherichia coli to express catalase, after which we explored an electrostatic adsorption approach to link black phosphorus quantum dots (BPQDs) to the surface of these bacteria, thereby generating an engineered E. coli/BPQDs (EB) system. Following intravenous injection, EB was able to target hypoxic tumor tissues. Subsequent 660 nm laser irradiation drove EB to generate reactive oxygen species (ROS) and destroy the membranes of these bacteria, leading to the release of catalase that subsequently degrades hydrogen peroxide to yield oxygen. Increased oxygen levels alleviate intratumoral hypoxia, thereby enhancing BPQD-mediated photodynamic therapy. This system was able to efficiently kill tumor cells in vivo, exhibiting good therapeutic efficacy. In summary, this study is the first to report the utilization of engineered bacteria to facilitate PDT, and our results highlight new avenues for BPQD-mediated cancer treatment.

Gold nanobipyramid-loaded black phosphorus nanosheets for plasmon-enhanced photodynamic and photothermal therapy of deep-seated orthotopic lung tumors.

Various types of photodynamic agents have been explored for photodynamic therapy (PDT) to destroy cancers located in deep tissues. However, these agents are generally limited by low singlet oxygen (1O2) yields owing to weak absorption in the optical transparent window of biological tissues. Accordingly, in this work, we developed a nanocomposite through the assembly of gold nanobipyramids (GNBPs) on black phosphorus nanosheets (BPNSs). This nanocomposite could simultaneously enhance 1O2 generation and hyperthermia by localized surface plasmon resonance in cancer therapy. As two-dimensional inorganic photosensitizers, BPNSs were hybridized with GNBPs to form BPNS-GNBP hybrid nanosheets. The hybridization markedly increased 1O2 production by the BPNSs through plasmon-enhanced light absorption. The nanocomposite exhibited a higher photothermal conversion efficiency than the BPNSs alone. In vitro and in vivo assays indicated that the BPNS-GNBP hybrid nanocomposite exhibited good tumor inhibition efficacy owing to simultaneous dual-modality phototherapy. In vivo, the nanocomposite suppressed deep-seated tumor growth with minimal adverse effects in mice bearing orthotopic A549 human lung tumors. Taken together, these results demonstrated that our BPNS-GNBP nanocomposite could function as a promising dual-modality phototherapeutic agent for enhanced cancer therapy in future cancer treatments. STATEMENT OF SIGNIFICANCE: In this study, we established a new nanocomposite by assembly of gold nanobipyramids (GNBPs) on black phosphorus nanosheets (BPNSs). Characterization of this nanocomposite showed that BPNS-GNBP enhanced 1O2 generation and hyperthermia. BPNS-GNBP exhibited good tumor inhibition efficacy in vivo and in vitro owing to simultaneous dual-modal phototherapy functions. Moreover, BPNS-GNBP suppressed deep-seated tumor growth in vivo and did not show adverse effects in mice bearing orthotopic A549 human lung tumors. Overall, these results showed that BPNS-GNBP may be used as a promising dual-modal phototherapeutic agent for enhanced cancer therapy in future clinical applications.

Biodegradable Black Phosphorus-based Nanomaterials in Biomedicine: Theranostic Applications.

Ascribe to the unique two-dimensional planar nanostructure with exceptional physical and chemical properties, black phosphorous (BP) as the emerging inorganic twodimensional nanomaterial with high biocompatibility and degradability has been becoming one of the most promising materials of great potentials in biomedicine. The exfoliated BP sheets possess ultra-high surface area available for valid bio-conjugation and molecular loading for chemotherapy. Utilizing the intrinsic near-infrared optical absorbance, BPbased photothermal therapy in vivo, photodynamic therapy and biomedical imaging has been realized, achieving unprecedented anti-tumor therapeutic efficacy in animal experiments. Additionally, the BP nanosheets can strongly react with oxygen and water, and finally degrade to non-toxic phosphate and phosphonate in the aqueous solution. This manuscript aimed to summarize the preliminary progresses on theranostic application of BP and its derivatives black phosphorus quantum dots (BPQDs), and discussed the prospects and the state-of-art unsolved critical issues of using BP-based material for theranostic applications.

Active waveguides written by femtosecond laser irradiation in an erbium-doped phospho-tellurite glass.

We report on fs-laser micromachining of active waveguides in a new erbium-doped phospho-tellurite glass by means of a compact cavity-dumped Yb-based writing system. The spectroscopic properties of the glass were investigated, and the fs-laser written waveguides were characterized in terms of passive as well as active performance. In particular, internal gain was demonstrated in the whole C+L band of optical communications (1530- 1610 nm).

Optimization of Pr3+, Tb3+, and Sm3+ co-doped (Y0.65Gd0.35)BO3:Eu0.05(3+) VUV phosphors through combinatorial approach.

A combinatorial approach was used to systematically investigate the effect of trace Pr(3+), Tb(3+), or Sm(3+) on the VUV photoluminescence of Eu(3+) in the Pr(3+), Tb(3+), or Sm(3+) co-doped (Y(0.65)Gd(0.35))BO(3):E(3+)(0.05). We found that Pr(3+) and Tb(3+)increases the VUV photoluminescent efficiency, while Sm(3+) decreases the efficiency. The optimized composition was identified to be between 7 x 10(-6) and 3 x 10(-4), and the corresponding efficiency improvement is about 15%. Scale-up experiments confirmed the results in the combinatorial materials libraries.

Long-term fade study of the DT-702 LiF: Mg,Cu,P TLD.

LiF thermoluminescent dosemeters (TLDs) are used by the US Navy to record radiation exposure of personnel. The Model DT-648 LiF:Mg,Ti TLD has been replaced by a new Model DT-702 LiF:Mg,Cu,P TLD. The DT-648 was used for many years and has undergone extensive testing to identify its pre- and post-irradiation fade operating characteristics. Studies have shown that the addition of copper increases the thermoluminesence sensitivity of the TLD for improved low-level radiation monitoring. This study evaluates various fading characteristics of the new copper-doped dosemeter using current equipment for processing of TLDs and calibrating to a National Institute of Standards and Technology standard source. The 57-week study took place at the Naval Dosimetry Center, Bethesda, MD, USA. TLDs were stored for various lengths of time before and after being exposed to a National Institute of Standards and Technology calibrated radiation sources. TLDs were then processed using current US Navy instructions and the resulting dose compared with the calibrated exposure. Both loss of signal and loss of sensitivity were evaluated. The results of this study have shown that the DT-702 TLD has no statistically significant change in sensitivity or change in signal with up to 57 weeks of pre- or post-irradiation time. The results of this study will increase the accuracy of exposure record keeping for the Navy and will allow longer issue periods. This will increase flexibility with international and domestic shipping procedures, as well as reduce workload requirements for dosimetry processing.

The use of photostimulable phosphor systems for periodic quality assurance in radiotherapy.

The fusion of radiological and optical images can be achieved through charging a photostimulable phosphor plate (PSP) with an exposure to a field of X- or gamma-rays, followed by exposure to an optical image which discharges the plate in relation to the amount of incident light. According to this PSP characteristic, we developed a simple method for periodic quality assurance (QA) of light/radiation field coincidence, distance indicator, field size indicators, crosshair centering, coincidence of radiation and mechanical isocenter for linear accelerators. The geometrical accuracy of radiological units can be subjected to the same QA method. Further, the source position accuracy for an HDR remote afterloader can be checked by taking an autoradiography of the radioactive source and simultaneously an optical image of a reference geometrical system.

Significantly enhanced visible light photocatalytic efficiency of phosphorus doped TiO2 with surface oxygen vacancies for ciprofloxacin degradation: Synergistic effect and intermediates analysis.

In the present work, we reported a simple method for the simultaneous phosphorus (P) doping and oxygen vacancies creation on TiO2 in a single step. The obtained P-doped TiO2 with surface oxygen vacancies (PTSOV) samples exhibited efficient photocatalytic activity for the degradation of fluoroquinolone antibacterial agent (ciprofloxacin) under visible light irradiation. The optimized sample showed a rate constant of 0.065 min-1 for degradation of ciprofloxacin (CIP) and it was about 16.2 times as high as that of TiO2 (0.004 min-1). The transformation products of CIP were identified by liquid chromatography-mass spectrometry (LC-MS), and degradation pathway was tentatively proposed. The doping state of P and the formation of surface oxygen vacancies (SOVs) were investigated by different methods. X-ray diffraction (XRD) and X-ray Photoemission Spectroscopy (XPS) revealed P5+ doped via formation TiOP bond. Electron paramagnetic resonance (EPR) spectroscopy revealed that SOVs were generated on P-doped TiO2. It turned out that the synergistic effect between doping P and SOVs on TiO2 greatly improved transfer and separation efficiency of photogenerated charges, thus significantly enhanced the visible light photocatalytic performance of TiO2. Our work would provide an effective way to design new photocatalysts with high performance under visible light irradiation.

Construction of plasmonic Ag modified phosphorous-doped ultrathin g-C3N4 nanosheets/BiVO4 photocatalyst with enhanced visible-near-infrared response ability for ciprofloxacin degradation.

To realize the full utilization of solar energy, the design of highly efficient photocatalyst with improved visible-near-infrared photocatalysis performance has attracted great attentions for environment pollutant removal. In this work, we rationally employed the surface plasmon resonance effect of metallic Ag in the phosphorus doped ultrathin g-C3N4 nanosheets (PCNS) and BiVO4 composites to construct a ternary Ag@PCNS/BiVO4 photocatalyst. It was applied for the photodegradation of ciprofloxacin (CIP), exhibiting 92.6% removal efficiency under visible light irradiation (λ>420nm) for 10mg/L CIP, and presenting enhanced photocatalytic ability than that of single component or binary nanocomposites under near-infrared light irradiation (λ>760nm). The improved photocatalytic activity of the prepared Ag@PCNS/BiVO4 nanocomposite can be attributed to the synergistic effect among the PCNS, BiVO4 and Ag, which not only improves the visible light response ability and hinders the recombination efficiency of the photogenerated electrons and holes, but also retains the strong the redox ability of the photogenerated charges. According to the trapping experiment and ESR measurements results, OH, h+ and O2- all participated in the photocatalytic degradation process. Considering the SPR effect of metallic Ag and the established local electric field around the interfaces, a dual Z-scheme electrons transfer mechanism was proposed.

Dose response of BaFBrl: Eu2+ storage phosphor plates exposed to megavoltage photon beams.

The BaFBrI:Eu2+ storage phosphor plate (SPP) is a reusable radiation image detector, widely used in diagnostic computed radiography, x-ray crystallography and radioactive tracer studies. When exposed to ionizing radiation, the SPP stores a latent image until it is scanned with a red reading laser which causes blue photostimulated luminescent (PSL) photons to be emitted. The mechanism of formation of the latent image is still poorly understood, especially for megavoltage photon beams. In order to gain insight into this mechanism and aid applications to high-energy beam dosimetry, the authors have directly determined the SPP generation efficiency, W, the energy required to produce one quantum of emitted PSL when it is irradiated by 60Co and 6 MV photon beams. This was done in four steps: 1. The SPP, in a water-equivalent plastic (WEP) phantom, was exposed to a 60Co or 6 MV beam, which had been calibrated to give a known absorbed dose to water in a water phantom at the position of the sensitive layer of the SPP. 2. Monte Carlo simulations were used to calculate the ratio of the dose to the sensitive layer in the WEP phantom to the dose to water at the same position in a water phantom. 3. A bleaching experiment was used to determine the number of photons emitted by a plate given a known dose. 4. The generation efficiency was calculated from the number of photons and the dose. This method is much more direct than previous calculations for kilovoltage x-ray beams based on quantum noise analysis. W was found, within experimental uncertainty, to be 190 eV for 60Co and 160 eV for 6 MV, independent of dose. The values for kilovoltage x-ray beams determined previously agree, within their large uncertainty, with these values for megavoltage beams.

Comparative study of LiF:Mg,Cu,Na,Si and Li2B4O7:Cu,Ag,P TL detectors.

Recently, two new types of 'tissue equivalent' thermoluminescent detectors (TLDs) have aroused attention: LiF:Mg,Cu,Na,Si and Li2B4O7:Cu,Ag,P. In this work the characteristics of both detectors were compared with the characteristics of the well-known type LiF:Mg,Ti detector, TLD-100. The following properties were investigated: the glow curve structures, relative sensitivity, batch homogeneity and uniformity, detection threshold, reproducibility of the response, linearity in the wide dose range and fading. Also, the energy dependence for medium and low energy X rays was determined in the range of mean energies between 33 and 116 keV. The results confirmed 'tissue equivalency' of both new types in the investigated range of photon energies. LiF:Mg,Cu,Na,Si detector has very high sensitivity (approximately 75 times higher than that of TLD-100) and is convenient for use in a very low range of doses. Li2B4O7:Cu,Ag,P detector shows some improvements in comparison with the previously prepared types of lithium borate. The most important is the five times higher sensitivity than that of TLD-100. This detector is also very promising, especially in medical dosimetry.

The application of LiF:Mg,Cu,P to large scale personnel dosimetry: current status and future directions.

LiF:Mg,Cu,P is starting to replace LiF:Mg,Ti in a variety of personnel dosimetry applications. LiF:Mg,Cu,P has superior characteristics as compared to LiF:Mg,Ti including, higher sensitivity, improved energy response for photons, lack of supralinearity and insignificant fading. The use of LiF:Mg,Cu,P in large scale dosimetry programs is of particular interest due to the extreme sensitivity of this material to the maximum readout temperature, and the variety of different dosimetry aspects and details that must be considered for a successful implementation in routine dosimetry. Here we discuss and explain the various aspects of large scale LiF:Mg,Cu,P based dosimetry programs including the properties of the TL material, new generation of TLD readers, calibration methodologies, a new generation of dose calculation algorithms based on the use of artificial neural networks and the overall uncertainty of the dose measurement. The United States Navy (USN) will be the first US dosimetry processor who will use this new material for routine applications. Until June 2002, the Navy used two types of thermoluminescent materials for personnel dosimetry, CaF2:Mn and LiF:Mg,Ti. A program to upgrade the system and to implement LiF:Mg,Cu,P, started in the mid 1990s and was recently concluded. In 2002, the new system replaced the LiF:Mg,Ti and is scheduled to start replacing the CaF2:Mn system in 2006. A pilot study to determine the dosimetric performance of the new LiF:Mg,Cu,P based dosimetry system was recently completed, and the results show the new system to be as good or better than the current system in all areas tested. As a result, LiF:Mg,Cu,P is scheduled to become the primary personnel dosimeter for the entire US Navy in 2006.

Determination of LiF:Mg,Ti and LiF:Mg,Cu,P TL efficiency for X-rays and their application to Monte Carlo simulations of dosemeter response.

The simulation of response of a new passive area dosemeter for measuring ambient dose equivalent H*(10) for photons has been performed using the Monte Carlo code MCNP and experimentally determined responses of LiF:Mg,Ti and LiF:Mg,Cu,P thermoluminescent (TL) detectors for hard-filtered X-ray spectra from 20 to 300 keV and for 137Cs and 60Co gamma radiation. Relative TL efficiency for both types of detectors, determined in experiments with bare detectors and similar Monte Carlo simulations, compared favourably with prediction of microdosimetric models for proposed microdosimetric target sizes in the range of 20-40 nm. The concluding verification experiment showed small deviations between measured and simulated dosemeter energy response values in the range of a few percent.

Optical absorption, TL and IRSL of basic plagioclase megacrysts from the pinacate (Sonora, Mexico) quaternary alkalic volcanics.

The paper presents the first results of an investigation on optical absorption (OA), thermally and infrared stimulated luminescence (TL and IRSL) of the Pinacate plagioclase (labradorite). The OA spectra reveal two bands with maxima at 1.0 and 3.2 eV connected with absorption of the Fe3+ and Fe2+ and IR absorption at wavelengths longer than 2700 nm. The ultraviolet absorption varies exponentially with the photon energy following the 'vitreous' empirical Urbach rule indicating exponential distribution of localised states in the forbidden band. The natural TL is peaked at 700 K. Laboratory beta irradiation creates a very broad TL peak with maximum at 430 K. The change of the 430 K TL peak shape under the thermal cleaning procedure and dark storage after irradiation reveals a monotonous increasing of the activation energy that can be explained by the exponential distribution of traps. The IRSL response is weak and exhibits a typical decay behaviour.

Time-resolved spectroscopy of LiF:Mg,Cu,P.

Time-resolved spectroscopy measurements of LiF:Mg,Cu,P luminescence are presented to obtain a better understanding of the emission characteristics of this material. The intensities and decay of the emission bands were studied as a function of annealing temperature and ionising radiation (gamma) dose. Two peaks in the emission were observed at 367 and 466 nm when excited by the 266 nm laser radiation. The luminescence spectrum under band-to-band X-ray excitation shows a dominant emission approximately 390-400 nm, which resembles the reported thermoluminescence emission and is clearly different from the spectrum obtained using the 266 nm pulsed laser excitation. Annealing of the material to 300 degrees C increases the intensity of the 367 and 466 nm emission bands by an order of magnitude as well as changes the relative intensity of the bands. Additional emission bands, which are not evident in the thermoluminescence emission spectra, are seen at longer wavelengths that also increase with dose. Possible explanations for the observed emission spectra are discussed in this paper.