Zeolitic imidazolate framework-8 modified magnetic halloysite nanotube-based solid phase extraction for the analysis of carbamate pesticides by ultra-high performance liquid chromatography tandem mass spectrometry.

Zeolitic imidazolate framework-8 modified magnetic halloysite nanotube (MHNTs@ZIF-8) composites were synthesized and evaluated for the first time as an efficient sorbent for the magnetic solid-phase extraction (mSPE) of carbamate pesticides (CPs) from water samples. MHNTs were prepared by coprecipitation, and MHNTs@ZIF-8 composites were assembled in situ at room temperature. After characterization, MHNTs@ZIF-8 was used to extract pirimicarb, propoxur, carbaryl, isoprocarb and fenobucarb via π-π stacking interaction and hydrophobic interaction between the imidazole skeleton of ZIF-8 and benzene rings or benzene-like rings in CPs, as well as the hydrogen bond formed between O in CPs and H in ZIF-8. The effects of the amount of sorbent, ionic strength, type and volume of desorption solvent and adsorption/desorption time were investigated. Under optimum conditions, good linearity was obtained for the analysis of CPs by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) with R2 ≥ 0.9992. The limits of quantification range from 3 to 40 ng L-1 in water. Relative standard deviations (RSDs) were <7%, n = 5, within a batch and <9% among batches. The spiked recoveries were between 81 and 104%. The proposed method has been successfully applied to the determination of CPs in various water samples.

Sulfonated halloysite nanotubes as a novel cation exchange material for solid phase extraction of toxic pyrrolizidine alkaloids.

Pyrrolizidine alkaloids are phytochemicals, which present a highly toxic class of compounds in multiple food resources and are therefore a late-breaking topic in food safety. This study describes the first use of modified halloysite nanotubes as a novel solid material for solid phase extraction. As a result of a fast one-pot sulfonation of the cheap and non-toxic halloysite nanotubes, an efficient cation exchange phase has been prepared. After optimization of the solid phase extraction protocol, high extraction efficiencies and overall recoveries were obtained for a mixture of four pyrrolizidine alkaloid structures through UHPLC-MS/MS analysis with caffeine as the internal standard. Furthermore, the novel solid phase was used for the selective binding of the toxic pyrrolizidine alkaloids in a real-life honey sample, which itself is often contaminated with these compounds. In-house validation showed great extraction efficiencies up to 99.9% for senecionine with a lower limit for lycopsamine with 59.3%, which indicated high selectivity even in the presence of potential interfering compounds. Subsequently, overall recoveries up to 91.5% could be obtained for senecionine while the lowest value was reached for lycopsamine with 55.1%. Comparison with a commercial strong cation exchange tube procedure showed the high competitiveness of the novel solid phase with respect to overall performance. Only slight disadvantages regarding precision and repeatability with values under 5.7% and 11.6% could be observed. Therefore, sulfonated halloysite nanotubes present themselves as an easy to prepare, cheap and highly efficient novel cation exchange material for the selective solid phase extraction of toxic pyrrolizidine alkaloids in frequently contaminated real-life samples like honey.

MIL-101(Fe)@TiO2 nanotube composite material is used for the solid phase extraction of non-steroidal anti-inflammatory drugs under the synergy of multiple interactions.

Increasing the adsorption sites and effective interactions between sorbents and the targets can improve the solid-phase extraction (SPE) efficiency. Herein, based on the advantages of MOFs and TiO2 nanotubes (TiO2 NTs), an MIL-101(Fe)@TiO2 NT composite was prepared and applied to extract non-steroidal anti-inflammatory drugs (NSAIDs) from water samples coupled with high performance liquid chromatography (HPLC). Through characterization, it was established that MIL-101(Fe) was effectively composited on the surface and inside the TiO2 nanotubes, increasing effective adsorption sites. The obtained composite material well retains the structure and functional groups of the two original materials, and while retaining the original force with the target, it achieves a synergistic effect and produces more interactions with the target. Therefore, the extraction efficiency was greatly improved. The recovery efficiency reached 97.7-105.1% with an RSD of less than 6.71%, the detection limit was 0.1-0.2 µg L-1, and the linear range was 1-200 µg L-1 with a determination coefficient of 0.9972-0.9994. Owing to the stability of the two original materials, the composite material could be recycled and reused to extract NSAIDs up to 15 times without a loss of the recovery rate. Satisfactory results were obtained when it was used to extract NSAIDs from the Yellow River. These results indicate that the synthesized MIL-101(Fe)@TiO2 NT material is a promising sorbent to extract NSAIDs at trace concentrations with high efficiency and long lifetimes.

Time-resolved fluorescence determination of albumin using ZnGeO:Mn luminescence nanorods modified with polydopamine nanoparticles.

A novel time-resolved fluorescence (TRF) pobe is constructed to detect human serum albumin (HSA) by exploiting ZnGeO:Mn persistent luminescence nanorods (ZnGeO:Mn PLNRs) and polydopamine nanoparticles (PDA NPs). HSA-induced dynamic quenching leads to the fluorescence decrease of ZnGeO:Mn PLNRs, providing the basis for quantitative analysis of HSA. The excellent photo-thermal conversion performance of PDA NPs is helpful to the collision process between ZnGeO:Mn PLNRs and HSA, inducing significant improvement of sensitivity. HSA is quantified by measuring time-resolved fluorescence at 540 nm under excitation of 250-nm light. Under optimal conditions, HSA in the linear range 0.1-100 ng mL-1 are detected by this PDA-mediated ZnGeO:Mn probe with high sensitivity and selectivity, and the detection limit is 36 pg mL-1 (3σ/s). The RSD for the quantification of HSA (5 ng mL-1, n = 11) is 5.2%. The practicability of this TRF probe is confirmed by accurate monitoring HSA contents in urine samples, giving rise to satisfactory spiking recoveries of 96.2-106.0%.

Bioorthogonal SERS Nanotags as a Precision Theranostic Platform for in Vivo SERS Imaging and Cancer Photothermal Therapy.

Precise detection and effective treatment are crucial to prolong cancer patients' lives. Surface-enhanced Raman scattering (SERS) imaging coupled with photothermal therapy has been considered a precise and effective strategy for cancer theranostics. Nevertheless, Raman reporters employed in the literature usually possessed multiple shift peaks in the fingerprint region, which are overlapped with background signals from endogenous biological molecules. Herein, we fabricated a new kind of bioorthogonal Raman reporter and aptamer functionalized SERS nanotags. The SERS nanotags demonstrated a strong Raman signal at 2205 cm-1 in the biologically Raman-silent region and recognized MCF-7 breast cancer cells for Raman imaging with high specificity. Laser irradiation induced serious toxicity of MCF-7 cells due to the excellent photothermal capability of the SERS nanotags. After intravenous administration of the SERS nanotags, tumor Raman spectral detection and mapping in living mice were successfully achieved. Further in vivo antitumor experiments manifested that the aptamer-modified SERS nanotags significantly restrained tumor growth after laser irradiation with 99% inhibition rate and good biocompatibility. These results clearly revealed that the SERS nanotags could serve as a novel and precise theranostic platform for in vivo cancer diagnosis and photothermal therapy.

Polyvalent Nanoobjects for Precision Diagnostics.

As our ability to synthesize and modify nanoobjects has improved, efforts to explore nanotechnology for diagnostic purposes have gained momentum. The variety of nanoobjects, especially those with polyvalent properties, displays a wide range of practical and unique properties well suited for applications in various diagnostics. This review briefly covers the broad scope of multivalent nanoobjects and their use in diagnostics, ranging from ex vivo assays and biosensors to in vivo imaging. The nanoobjects discussed here include silica nanoparticles, gold nanoparticles, quantum dots, carbon dots, fullerenes, polymers, dendrimers, liposomes, nanowires, and nanotubes. In this review, we describe recent reports of novel applications of these various nanoobjects, particularly as polyvalent entities designed for diagnostics.

Intracellular speciation of gold nanorods alters the conformational dynamics of genomic DNA.

Gold nanorods are one of the most widely explored inorganic materials in nanomedicine for diagnostics, therapeutics and sensing1. It has been shown that gold nanorods are not cytotoxic and localize within cytoplasmic vesicles following endocytosis, with no nuclear localization2,3, but other studies have reported alterations in gene expression profiles in cells following exposure to gold nanorods, via unknown mechanisms4. In this work we describe a pathway that can contribute to this phenomenon. By mapping the intracellular chemical speciation process of gold nanorods, we show that the commonly used Au-thiol conjugation, which is important for maintaining the noble (inert) properties of gold nanostructures, is altered following endocytosis, resulting in the formation of Au(I)-thiolates that localize in the nucleus5. Furthermore, we show that nuclear localization of the gold species perturbs the dynamic microenvironment within the nucleus and triggers alteration of gene expression in human cells. We demonstrate this using quantitative visualization of ubiquitous DNA G-quadruplex structures, which are sensitive to ionic imbalances, as an indicator of the formation of structural alterations in genomic DNA.

Molecular fingerprinting of nanoparticles in complex media with non-contact photoacoustics: beyond the light scattering limit.

Optical instruments can probe physical systems even to the level of individual molecules. In particular, every molecule, solution, and structure such as a living cell has a unique absorption spectrum representing a molecular fingerprint. This spectrum can help identify a particular molecule from others or quantify its concentration; however, scattering limits molecular fingerprinting within a complex compound and must be overcome. Here, we present a new, non-contact photoacoustic (PA)-based method that can almost completely remove the influence of background light scattering on absorption measurements in heterogeneous highly scattering solutions and, furthermore, separate the intrinsic absorption of nanoscale objects from their scattering. In particular, we measure pure absorption spectra for solutions of gold nanorods (GNRs) as an example of a plasmonic agent and show that these spectra differ from the extinction measured with conventional UV-VIS spectrophotometry. Finally, we show how the original GNR absorption changes when nanoparticles are internalized by cells.

A nanoformulation for the preferential accumulation in adult neurogenic niches.

Stimulation of adult neurogenesis by targeting the endogenous neural stem cells (NSCs), located in hippocampus and subventricular zone (SVZ), with nanoformulations has been proposed for brain repair in cases of neurodegenerative diseases. Unfortunately, it is relatively unknown the nanoformulation properties to facilitate their accumulation in the neurogenic niches after intravenous injection. Here, we have screened different gold-based formulations having variable morphology, surface chemistry and responsiveness to light for their capacity to cross the blood brain barrier (BBB) and accumulate preferentially in the neurogenic niches. Results obtained in a human in vitro BBB model showed that gold nanoparticles (Au NPs) and gold nanorods (Au NRs) conjugated with medium density of transferrin (Tf) peptides (i.e. between 169 and 230 peptides per NP) crossed more efficiently the BBB than the remaining formulations. This is due to a relatively lower avidity of these formulations to Tf receptor (TfR) and lower accumulation in the lysosomes, as compared to the other formulations. We further show that the near infrared light (NIR) irradiation of Au NRs, under a certain concentration and at specific cell culture time, lead to the opening of the BBB. Finally, we demonstrate that Au NRs conjugated with Tf administered intravenously in mice and activated by NIR had the highest accumulation in the neurogenic niches. Our results open the possibility of targeting more effectively the neurogenic niches by controlling the properties of the nanoformulations.

Fabrication of a Flexible Gold Nanorod Polymer Metafilm via a Phase Transfer Method as a SERS Substrate for Detecting Food Contaminants.

Surface enhanced Raman scattering (SERS) has been widely used in detection of food safety due to the nondestructive examination property. Here, we reported a flexible SERS film based on a polymer-immobilized gold nanorod polymer metafilm. Polystyrene-polyisoprene-polystyrene (SIS), a transparent and flexible, along with having excellent elasticity, polymer, was chosen as the main support of gold nanorods. A simple phase transfer progress was adopted to mix the gold nanorods with the polymer, which can further be used in most water-insoluble polymers. The SERS film performed satisfactorily while being tested in a series of standard Raman probes, like crystal violet (CV) and malachite green (MG). Moreover, the excellent reproducibility and elastic properties make the film a promising substrate in practical detection. Hence, the MG detection on the fish surface and trace thiram detection on orange pericarp were inspected with detection results of 1 × 10-10 and 1 × 10-6 M, which were below the demand of the National standard of China, exactly matching the realistic application requirements.

Characteristic rotational behaviors of rod-shaped cargo revealed by automated five-dimensional single particle tracking.

We report an automated single particle tracking technique for tracking the x, y, z coordinates, azimuthal and elevation angles of anisotropic plasmonic gold nanorod probes in live cells. These five spatial coordinates are collectively referred to as 5D. This method overcomes a long-standing challenge in distinguishing rotational motions from translational motions in the z-axis in differential interference contrast microscopy to result in full disclosure of nanoscale motions with high accuracy. Transferrin-coated endocytic gold nanorod cargoes initially undergo active rotational diffusion and display characteristic rotational motions on the membrane. Then as the cargoes being enclosed in clathrin-coated pits, they slow down the active rotation and experience a quiet period before they restore active rotational diffusion after fission and eventually being transported away from the original entry spots. Finally, the 3D trajectories and the accompanying rotational motions of the cargoes are resolved accurately to render the intracellular transport process in live cells.Distinguishing rotational motions from translational motions in the z-axis has been a long-standing challenge. Here the authors develop a five-dimensional single particle tracking method to detect rotational behaviors of nanocargos during clathrin-mediated endocytosis and intracellular transport.

Multifunctional halloysite nanotubes for targeted delivery and controlled release of doxorubicin in-vitro and in-vivo studies.

The current state of cancer therapy encourages researchers to develop novel efficient nanocarriers. Halloysite nanotubes (HNTs) are good nanocarrier candidates due to their unique nanoscale (40-80 nm in diamter and 200-500 nm in length) and hollow lumen, as well as good biocompatibility and low cost. In our study, we prepared a type of folate-mediated targeting and redox-triggered anticancer drug delivery system, so that Doxorubicin (DOX) can be specifically transported to tumor sites due to the over-expressed folate-receptors on the surface of cancer cells. Furthermore, it can then be released by the reductive agent glutathione (GSH) in cancer cells where the content of GSH is nearly 103-fold higher than in the extracellular matrix. A series of methods have demonstrated that per-thiol-ß-cyclodextrin (ß-CD-(SH)7) was successfully combined with HNTs via a redox-responsive disulfide bond, and folic acid-polyethylene glycol-adamantane (FA-PEG-Ad) was immobilized on the HNTs through the strong complexation between ß-CD/Ad. In vitro studies indicated that the release rate of DOX raised sharply in dithiothreitol (DTT) reducing environment and the amount of released DOX reached 70% in 10 mM DTT within the first 10 h, while only 40% of DOX was released in phosphate buffer solution (PBS) even after 79 h. Furthermore, the targeted HNTs could be specifically endocytosed by over-expressed folate-receptor cancer cells and significantly accelerate the apoptosis of cancer cells compared to non-targeted HNTs. In vivo studies further verified that the targeted HNTs had the best therapeutic efficacy and no obvious side effects for tumor-bearing nude mice, while free DOX showed damaging effects on normal tissues. In summary, this novel nanocarrier system shows excellent potential for targeted delivery and controlled release of anticancer drugs and provides a potential platform for tumor therapy.

Zwitterionic gold nanorods: low toxicity and high photothermal efficacy for cancer therapy.

Novel "zwitterionic" gold nanorods (Au NRs) were constructed through a facile ligand exchange process between cetyltrimethylammonium bromide (CTAB)-Au NRs and the zwitterionic block polymer {poly(2-methacryloyloxyethyl phosohorylcholine)-b-poly(lipoic methacrylate) (pMPC-b-pLA)}. In vitro, they exhibited low dark cytotoxicity and a high therapeutic efficacy to cancer cells. Their blood circulation half-life in vivo (t1/2, ∼10 h) was 20-fold longer than that of CTAB-Au NRs (t1/2, <30 min). After intravenous administration, they accumulated in tumour sites via an enhanced permeability and retention (EPR) effect and enabled destruction of human xenograft tumours in mice after exposure of the tumour location to NIR laser irradiation at 808 nm. These studies showed that the "zwitterionic" Au NRs had low toxicity and high photothermal efficacy both in vitro and in vivo due to the suprahydrophilic, biocompatible zwitterionic polymer coating layer. They may have the potential to be a promising NIR PTT agent in the biomedical field.

Nanomechanical properties, wear resistance and in-vitro characterization of Ta2O5 nanotubes coating on biomedical grade Ti-6Al-4V.

Tantalum pentoxide nanotubes (Ta2O5 NTs) can dramatically raise the biological functions of different kinds of cells, thus have promising applications in biomedical fields. In this study, Ta2O5 NTs were prepared on biomedical grade Ti-6Al-4V alloy (Ti64) via physical vapor deposition (PVD) and a successive two-step anodization in H2SO4: HF (99:1)+5% EG electrolyte at a constant potential of 15V. To improve the adhesion of nanotubular array coating on Ti64, heat treatment was carried out at 450°C for 1h under atmospheric pressure with a heating/cooling rate of 1°Cmin-1. The surface topography and composition of the nanostructured coatings were examined by atomic force microscopy (AFM) and X-ray electron spectroscopy (XPS), to gather information about the corrosion behavior, wear resistance and bioactivity in simulated body fluids (SBF). From the nanoindentation experiments, the Young's modulus and hardness of the 5min anodized sample were ~ 135 and 6GPa, but increased to ~ 160 and 7.5GPa, respectively, after annealing at 450°C. It was shown that the corrosion resistance of Ti64 plates with nanotubular surface modification was higher than that of the bare substrate, where the 450°C annealed specimen revealed the highest corrosion protection efficiency (99%). Results from the SBF tests showed that a bone-like apatite layer was formed on nanotubular array coating, as early as the first day of immersion in simulated body fluid (SBF), indicating the importance of nanotubular configuration on the in-vitro bioactivity.

Toward improved mechanical, tribological, corrosion and in-vitro bioactivity properties of mixed oxide nanotubes on Ti-6Al-7Nb implant using multi-objective PSO.

Recently, the robust optimization and prediction models have been highly noticed in district of surface engineering and coating techniques to obtain the highest possible output values through least trial and error experiments. Besides, due to necessity of finding the optimum value of dependent variables, the multi-objective metaheuristic models have been proposed to optimize various processes. Herein, oriented mixed oxide nanotubular arrays were grown on Ti-6Al-7Nb (Ti67) implant using physical vapor deposition magnetron sputtering (PVDMS) designed by Taguchi and following electrochemical anodization. The obtained adhesion strength and hardness of Ti67/Nb were modeled by particle swarm optimization (PSO) to predict the outputs performance. According to developed models, multi-objective PSO (MOPSO) run aimed at finding PVDMS inputs to maximize current outputs simultaneously. The provided sputtering parameters were applied as validation experiment and resulted in higher adhesion strength and hardness of interfaced layer with Ti67. The as-deposited Nb layer before and after optimization were anodized in fluoride-base electrolyte for 300min. To crystallize the coatings, the anodically grown mixed oxide TiO2-Nb2O5-Al2O3 nanotubes were annealed at 440°C for 30min. From the FESEM observations, the optimized adhesive Nb interlayer led to further homogeneity of mixed nanotube arrays. As a result of this surface modification, the anodized sample after annealing showed the highest mechanical, tribological, corrosion resistant and in-vitro bioactivity properties, where a thick bone-like apatite layer was formed on the mixed oxide nanotubes surface within 10 days immersion in simulated body fluid (SBF) after applied MOPSO. The novel results of this study can be effective in optimizing a variety of the surface properties of the nanostructured implants.

Rhodococcus aetherivorans BCP1 as cell factory for the production of intracellular tellurium nanorods under aerobic conditions.

BACKGROUND: Tellurite (TeO32-) is recognized as a toxic oxyanion to living organisms. However, mainly anaerobic or facultative-anaerobic microorganisms are able to tolerate and convert TeO32- into the less toxic and available form of elemental Tellurium (Te0), producing Te-deposits or Te-nanostructures. The use of TeO32--reducing bacteria can lead to the decontamination of polluted environments and the development of "green-synthesis" methods for the production of nanomaterials. In this study, the tolerance and the consumption of TeO32- have been investigated, along with the production and characterization of Te-nanorods by Rhodococcus aetherivorans BCP1 grown under aerobic conditions. RESULTS: Aerobically grown BCP1 cells showed high tolerance towards TeO32- with a minimal inhibitory concentration (MIC) of 2800 µg/mL (11.2 mM). TeO32- consumption has been evaluated exposing the BCP1 strain to either 100 or 500 µg/mL of K2TeO3 (unconditioned growth) or after re-inoculation in fresh medium with new addition of K2TeO3 (conditioned growth). A complete consumption of TeO32- at 100 µg/mL was observed under both growth conditions, although conditioned cells showed higher consumption rate. Unconditioned and conditioned BCP1 cells partially consumed TeO32- at 500 µg/mL. However, a greater TeO32- consumption was observed with conditioned cells. The production of intracellular, not aggregated and rod-shaped Te-nanostructures (TeNRs) was observed as a consequence of TeO32- reduction. Extracted TeNRs appear to be embedded in an organic surrounding material, as suggested by the chemical-physical characterization. Moreover, we observed longer TeNRs depending on either the concentration of precursor (100 or 500 µg/mL of K2TeO3) or the growth conditions (unconditioned or conditioned grown cells). CONCLUSIONS: Rhodococcus aetherivorans BCP1 is able to tolerate high concentrations of TeO32- during its growth under aerobic conditions. Moreover, compared to unconditioned BCP1 cells, TeO32- conditioned cells showed a higher oxyanion consumption rate (for 100 µg/mL of K2TeO3) or to consume greater amount of TeO32- (for 500 µg/mL of K2TeO3). TeO32- consumption by BCP1 cells led to the production of intracellular and not aggregated TeNRs embedded in an organic surrounding material. The high resistance of BCP1 to TeO32- along with its ability to produce Te-nanostructures supports the application of this microorganism as a possible eco-friendly nanofactory.

Two-Step Mechanism of Cellular Uptake of Cationic Gold Nanoparticles Modified by (16-Mercaptohexadecyl)trimethylammonium Bromide.

Cationic colloidal gold nanorods (GNRs) have a great potential as a theranostic tool for diverse medical applications. GNRs' properties such as cellular internalization and stability are determined by physicochemical characteristics of their surface coating. GNRs modified by (16-mercaptohexadecyl)trimethylammonium bromide (MTAB), MTABGNRs, show excellent cellular uptake. Despite their promise for biomedicine, however, relatively little is known about the cellular pathways that facilitate the uptake of GNRs, their subcellular fate and intracellular persistence. Here we studied the mechanism of cellular internalization and long-term fate of GNRs coated with MTAB, for which the synthesis was optimized to give higher yield, in various human cell types including normal diploid versus cancerous, and dividing versus nondividing (senescent) cells. The process of MTABGNRs internalization into their final destination in lysosomes proceeds in two steps: (1) fast passive adhesion to cell membrane mediated by sulfated proteoglycans occurring within minutes and (2) slower active transmembrane and intracellular transport of individual nanorods via clathrin-mediated endocytosis and of aggregated nanorods via macropinocytosis. The expression of sulfated proteoglycans was the major factor determining the extent of uptake by the respective cell types. Upon uptake into proliferating cells, MTABGNRs were diluted equally and relatively rapidly into daughter cells; however, in nondividing/senescent cells the loss of MTABGNRs was gradual and very modest, attributable mainly to exocytosis. Exocytosed MTABGNRs can again be internalized. These findings broaden our knowledge about cellular uptake of gold nanorods, a crucial prerequisite for future successful engineering of nanoparticles for biomedical applications such as photothermal cancer therapy or elimination of senescent cells as part of the emerging rejuvenation approach.

Vesicle Size Regulates Nanotube Formation in the Cell.

Intracellular membrane nanotube formation and its dynamics play important roles for cargo transportation and organelle biogenesis. Regarding the regulation mechanisms, while much attention has been paid on the lipid composition and its associated protein molecules, effects of the vesicle size has not been studied in the cell. Giant unilamellar vesicles (GUVs) are often used for in vitro membrane deformation studies, but they are much larger than most intracellular vesicles and the in vitro studies also lack physiological relevance. Here, we use lysosomes and autolysosomes, whose sizes range between 100 nm and 1 µm, as model systems to study the size effects on nanotube formation both in vivo and in vitro. Single molecule observations indicate that driven by kinesin motors, small vesicles (100-200 nm) are mainly transported along the tracks while a remarkable portion of large vesicles (500-1000 nm) form nanotubes. This size effect is further confirmed by in vitro reconstitution assays on liposomes and purified lysosomes and autolysosomes. We also apply Atomic Force Microscopy (AFM) to measure the initiation force for nanotube formation. These results suggest that the size-dependence may be one of the mechanisms for cells to regulate cellular processes involving membrane-deformation, such as the timing of tubulation-mediated vesicle recycling.

Contrast-enhanced optical coherence tomography with picomolar sensitivity for functional in vivo imaging.

Optical Coherence Tomography (OCT) enables real-time imaging of living tissues at cell-scale resolution over millimeters in three dimensions. Despite these advantages, functional biological studies with OCT have been limited by a lack of exogenous contrast agents that can be distinguished from tissue. Here we report an approach to functional OCT imaging that implements custom algorithms to spectrally identify unique contrast agents: large gold nanorods (LGNRs). LGNRs exhibit 110-fold greater spectral signal per particle than conventional GNRs, which enables detection of individual LGNRs in water and concentrations as low as 250 pM in the circulation of living mice. This translates to ~40 particles per imaging voxel in vivo. Unlike previous implementations of OCT spectral detection, the methods described herein adaptively compensate for depth and processing artifacts on a per sample basis. Collectively, these methods enable high-quality noninvasive contrast-enhanced imaging of OCT in living subjects, including detection of tumor microvasculature at twice the depth achievable with conventional OCT. Additionally, multiplexed detection of spectrally-distinct LGNRs was demonstrated to observe discrete patterns of lymphatic drainage and identify individual lymphangions and lymphatic valve functional states. These capabilities provide a powerful platform for molecular imaging and characterization of tissue noninvasively at cellular resolution, called MOZART.

Anodic fabrication of advanced titania nanotubes photocatalysts for photoelectrocatalysis decolorization of Orange G dye.

Titania nanotubes (TNTs) were fabricated on Ti mesh substrates by the anodizing technique. The effects of preparation variables, such as anodizing voltage, time and calcination temperature on the textural characteristics and photocatalytic activity of TNTs were investigated. The surface morphology, crystalline phase, and chemical composition were analyzed using field emission-scanning electron microscopy and X-ray diffraction. The photo-electrochemical properties of TNTs were examined by voltammetry. The TNTs were tested as a photoanode for advanced oxidation processes, such as photocatalytic, electrocatalytic, and photoelectrocatalytic decolorization of Orange G dye. The well-arranged TNTs electrode prepared in this work showed a high photocurrent density of 101 µA cm(-2) at an optimum length-to-diameter aspect ratio of 31.2. In dye decolorization tests, the electrochemical photocatalytic system using TNTs as the photoanode achieved total decolorization and 64% mineralization under extended reaction time. These results show that TNTs prepared by this method is greatly stable in prolonged use and suitable as a photoanode in the photocatalytic/photoelectrocatalytic treatments of dye wastewater.