Protein‐Enabled Layer‐by‐Layer Syntheses of Aligned,Porous‐Wall,High‐Aspect‐Ratio TiO2 Nanotube Arrays

An aqueous, protein‐enabled (biomimetic), layer‐by‐layer titania deposition process is developed, for the first time, to convert aligned‐nanochannel templates into high‐aspect‐ratio, aligned nanotube arrays with thin (34 nm) walls composed of co‐continuous networks of pores and titania nanocrystals (15 nm ave. size). Alumina templates with aligned open nanochannels are exposed in an alternating fashion to aqueous protamine‐bearing and titania precursor‐bearing (Ti(IV) bis‐ammonium‐lactato‐dihydroxide, TiBALDH) solutions. The ability of protamine to bind to alumina and titania, and to induce the formation of a Ti–O‐bearing coating upon exposure to the TiBALDH precursor, enables the layer‐by‐layer deposition of a conformal protamine/Ti–O‐bearing coating on the nanochannel surfaces within the porous alumina template. Subsequent protamine pyrolysis yields coatings composed of co‐continuous networks of pores and titania nanoparticles. Selective dissolution of the underlying alumina template through the porous coating then yields freestanding, aligned, porous‐wall titania nanotube arrays. The interconnected pores within the nanotube walls allow enhanced loading of functional molecules (such as a Ru‐based N719 dye), whereas the interconnected titania nanoparticles enable the high‐aspect‐ratio, aligned nanotube arrays to be used as electrodes (as demonstrated for dye‐sensitized solar cells with power conversion efficiencies of 5.2 ± 0.4%).     

Titania Nanotubes: Protein‐Enabled Layer‐by‐Layer Syntheses of Aligned,Porous‐Wall,High‐Aspect‐Ratio TiO2 Nanotube Arrays (Adv. Funct. Mater. 9/2011)

An aqueous, protein‐enabled (biomimetic), layer‐by‐layer titania deposition process is developed, for the first time, to convert aligned‐nanochannel templates into high‐aspect‐ratio, aligned nanotube arrays with thin (34 nm) walls composed of co‐continuous networks of pores and titania nanocrystals (15 nm ave. size). Alumina templates with aligned open nanochannels are exposed in an alternating fashion to aqueous protamine‐bearing and titania precursor‐bearing (Ti(IV) bis‐ammonium‐lactato‐dihydroxide, TiBALDH) solutions. The ability of protamine to bind to alumina and titania, and to induce the formation of a Ti–O‐bearing coating upon exposure to the TiBALDH precursor, enables the layer‐by‐layer deposition of a conformal protamine/Ti–O‐bearing coating on the nanochannel surfaces within the porous alumina template. Subsequent protamine pyrolysis yields coatings composed of co‐continuous networks of pores and titania nanoparticles. Selective dissolution of the underlying alumina template through the porous coating then yields freestanding, aligned, porous‐wall titania nanotube arrays. The interconnected pores within the nanotube walls allow enhanced loading of functional molecules (such as a Ru‐based N719 dye), whereas the interconnected titania nanoparticles enable the high‐aspect‐ratio, aligned nanotube arrays to be used as electrodes (as demonstrated for dye‐sensitized solar cells with power conversion efficiencies of 5.2 ± 0.4%).     

High Temperature Crystallization of Free‐Standing Anatase TiO2 Nanotube Membranes for High Efficiency Dye‐Sensitized Solar Cells

Despite the one‐dimensional ordering of anodic TiO₂ nanotube arrays (TNAs), the electron diffusion towards the substrate in TNA‐based dye‐sensitized solar cells (DSSCs) is comparably slow. The improvement of electron mobility by enhancing TNA crystallinity under high‐temperature annealing, however, is infeasible with the existence of Ti metal substrate. Herein, it is shown that, by high temperature (up to 700 °C) crystallization of high‐quality free‐standing TNA membranes, the TNAs can maintain their structure integrity and phase (anatase) stability as a result of the absence of the nucleation sites and the high quality of the membrane obtained by a self‐detachment method. The electron transport is much faster (≈4 times) in the 700 °C‐annealed TNA membranes than that in the 400 °C‐treated ones for 20 μm‐length nanotubes, which is mainly attributed to the improved crystallinity and reduced electron trap states. In spite of slightly reduced dye loading capacity (decreased by ≈30%) in the 700 °C‐annealed membranes, the superior electron transport leads to a significantly improved efficiency of 7.81% (enhanced by ≈50%). The strategy of manipulating the electron transport dynamics by high temperature treatment on high‐quality TNA membranes may open new route for further improvement in the performances of TNA‐based DSSCs.     

Hexagonal Network Organization of Dye‐Loaded Zeolite L Crystals by Surface‐Tension Driven Autoassembly

Highly fluorescent dye‐loaded zeolite L crystals, approximately 1.4 μm long and 650 nm in diameter, are organized in a hexagonal network by a surface‐tension‐driven autoassembly process. A polydimethylsiloxane (PDMS) film presenting a trigonal ordering of spherical protuberances, including a polystyrene (PS) hexagonal network occupying their interstices, is chosen as the platform for the assembly. The overall wettability and the difference in surface tension between PDMS and PS surfaces are found to offer good conditions for ordering micrometric dye‐loaded zeolite L crystals in a 2D hexagonal network. The resulting film displays a regular hexagonal pattern of polarized fluorescence, reflecting the polarization properties of the dye molecules inserted in the parallel nanochannels of the zeolites.     

Integrated Photo‐supercapacitor Based on Bi‐polar TiO2 Nanotube Arrays with Selective One‐Side Plasma‐Assisted Hydrogenation

One‐dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as electrode materials for both dye‐sensitized solar cells (DSSCs) and electrochemical supercapacitors (SCs). In this work, a novel stack‐integrated photo‐supercapacitor (PSC) thin‐film device is presented, composed of a DSSC and a SC built on bi‐polar ATO nanotube arrays, where an improved SC performance is achieved through selective plasma‐assisted hydrogenation treatment. At a high current density of 1 mA/cm² in charge/discharge measurements, the areal capacitance of selective hydrogenated ATO two‐electrode sub‐device is substantially increased ～5.1 times, with the value as high as 1.100 mF/cm². The optimized PSC exhibits a remarkable overall photoelectric conversion and storage efficiency up to 1.64%, with fast response and superior cycling capability for more than 100 photocharge/galvanostatic discharge cycles without any decay. To meet applicable demands with a larger output voltage, a tandem PSC system is constructed, serving as the self‐driven power source for an LED.     

Tumor‐Penetrating Nanotherapeutics Loading a Near‐Infrared Probe Inhibit Growth and Metastasis of Breast Cancer

The tumor growth and metastasis is the leading reason for the high mortality of breast cancer. Herein, it is first reported a deep tumor‐penetrating photothermal nanotherapeutics loading a near‐infrared (NIR) probe for potential photothermal therapy (PTT) of tumor growth and metastasis of breast cancer. The NIR probe of 1,1‐dioctadecyl‐3,3,3,3‐tetramethylindotricarbocyanine iodide (DiR), a lipophilicfluorescent carbocyanine dye with strong light‐absorbing capability, is entrapped into the photothermal nanotherapeutics for PTT application. The DiR‐loaded photothermal nanotherapeutics (DPN) is homogeneous nanometer‐sized particles with the mean diameter of 24.5 ± 4.1 nm. Upon 808 nm laser irradiation, DPN presents superior production of thermal energy than free DiR both in vitro and in vivo. The cell proliferation and migration activities of metastatic 4T1 breast cancer cells are obviously inhibited by DPN in combination with NIR irradiation. Moreover, DPN can induce a higher accumulation in tumor and penetrate into the deep interior of tumor tissues. The in vivo PTT measurements indicate that the growth and metastasis of breast cancer are entirely inhibited by a single treatment of DPN with NIR irradiation. Therefore, the deep tumor‐penetrating DPN can provide a promising strategy for PTT of tumor progression and metastasis of breast cancer.     

Carbon‐Nanotube‐Templated Microfabrication of Porous Silicon‐Carbon Materials with Application to Chemical Separations

Carbon‐nanotube‐templated microfabrication (CNT‐M) of porous materials is demonstrated. Partial chemical infiltration of 3D carbon‐nanotube structures with silicon results in a mechanically robust material, structured from the 10 nm scale to the 100 μm scale. The nanoscale dimensions are determined by the diameter and spacing of the resulting silicon/carbon nanotubes, while the microscale dimensions are controlled by the lithographic patterning of the CNT growth catalyst. We demonstrate the utility of this hierarchical structuring approach by using CNT‐M to fabricate thin‐layer‐chromatography (TLC) separations media with precise microscale channels for fluid‐flow control and nanoscale porosity for high analyte capacity. Chemical separations done on the CNT‐M‐structured media outperform commercial high‐performance TLC media.     

Bench‐Top Fabrication of Hierarchically Structured High‐Surface‐Area Electrodes

Fabrication of hierarchical materials, with highly optimized features from the millimeter to the nanometer scale, is crucial for applications in diverse areas including biosensing, energy storage, photovoltaics, and tissue engineering. In the past, complex material architectures have been achieved using a combination of top‐down and bottom‐up fabrication approaches. A remaining challenge, however, is the rapid, inexpensive, and simple fabrication of such materials systems using bench‐top prototyping methods. To address this challenge, the properties of hierarchically structured electrodes are developed and investigated by combining three bench‐top techniques: top‐down electrode patterning using vinyl masks created by a computer‐aided design (CAD)‐driven cutter, thin film micro/nanostructuring using a shrinkable polymer substrate, and tunable electrodeposition of conductive materials. By combining these methods, controllable electrode arrays are created with features in three distinct length scales: 40 μm to 1 mm, 50 nm to 10 μm, and 20 nm to 2 μm. The electrical and electrochemical properties of these electrodes are analyzed and it is demonstrated that they are excellent candidates for next generation low‐cost electrochemical and electronic devices.     

Template‐Directed Liquid ALD Growth of TiO2 Nanotube Arrays: Properties and Potential in Photovoltaic Devices

Dense and well‐aligned arrays of TiO₂ nanotubes extending from various substrates are successfully fabricated via a new liquid‐phase atomic layer deposition (LALD) in nanoporous anodic alumina (AAO) templates followed by alumina dissolution. The facile and versatile process circumvents the need for vacuum conditions critical in traditional gas‐phase ALD and yet confers ALD‐like deposition rates of 1.6–2.2 Å cycle^?1, rendering smooth conformal nanotube walls that surpass those achievable by sol–gel and Ti‐anodizing techniques. The nanotube dimensions can be tuned, with most robust structures being 150–400 nm tall, 60–70 nm in diameter with 5–20 nm thick walls. The viability of TiO₂ nanotube arrays deposited on indium tin oxide (ITO)–glass electrodes for application in model hybrid poly(3‐hexylthiophene) (P3HT):TiO₂ solar cells is studied. The results achieved provide platforms and research directions for further advancements.     

A Multiwalled‐Carbon‐Nanotube‐Based Biosensor for Monitoring Microcystin‐LR in Sources of Drinking Water Supplies

A multiwalled carbon nanotube (MWCNT)‐based electrochemical biosensor is developed for monitoring microcystin‐LR (MC‐LR), a toxic cyanobacterial toxin, in sources of drinking water supplies. The biosensor electrodes are fabricated using vertically well‐aligned, dense, millimeter‐long MWCNT arrays with a narrow size distribution, grown on patterned Si substrates by water‐assisted chemical vapor deposition. High temperature thermal treatment (2500 °C) in an Ar atmosphere is used to enhance the crystallinity of the pristine materials, followed by electrochemical functionalization in alkaline solution to produce oxygen‐containing functional groups on the MWCNT surface, thus providing the anchoring sites for linking molecules that allow the immobilization of MC‐LR onto the MWCNT array electrodes. Addition of the monoclonal antibodies specific to MC‐LR in the incubation solutions offers the required sensor specificity for toxin detection. The performance of the MWCNT array biosensor is evaluated using micro‐Raman spectroscopy, including polarized Raman measurements, X‐ray photoelectron spectroscopy, cyclic voltammetry, optical microscopy, and Faradaic electrochemical impedance spectroscopy. A linear dependence of the electron‐transfer resistance on the MC‐LR concentration is observed in the range of 0.05 to 20 μg L^?1, which enables cyanotoxin monitoring well below the World Health Organization (WHO) provisional concentration limit of 1 μg L^?1 for MC‐LR in drinking water.     

A Near‐Infrared cis‐Configured Squaraine Co‐Sensitizer for High‐Efficiency Dye‐Sensitized Solar Cells

A cis‐configured squaraine dye (HSQ1), synthesized by incorporation of a strongly electron‐withdrawing dicyanovinyl group into the central squaric acid moiety, is employed in dye‐sensitized solar cells (DSCs). In solution, HSQ1 displays an intense absorption in the near‐infrared region with a maximum at 686 nm and when the dye is adsorbed on a TiO₂ surface, the absorption spectrum broadens in both the blue and the near‐infrared regions, which is favorable for efficient light harvesting over a broad wavelength range. A solar cell sensitized with HSQ1 shows a broader incident photon‐to‐current conversion efficiency (IPCE) spectrum (from 400 to 800 nm) and a higher IPCE in the long‐wavelength region (71% at 700 nm) than a cell sensitized with squaraine dye SQ1. Furthermore, a solar cell co‐sensitized with HSQ1 and N3 dye shows remarkably improved short‐circuit current density and open‐circuit voltage compared to those of a DSC based on N3 alone and fabricated under the same conditions. The energy‐conversion efficiency of the co‐sensitized DSC is 8.14%, which is the highest reported efficiency for a squaraine dye–based co‐sensitized DSC without using Al₂O₃ layer.     

pH‐Responsive Cyanine‐Grafted Graphene Oxide for Fluorescence Resonance Energy Transfer‐Enhanced Photothermal Therapy

Stimuli‐responsive anticancer agents are of particular interest in the field of cancer therapy. Nevertheless, so far stimuli‐responsive photothermal agents have been explored with limited success for cancer photothermal therapy (PTT). In this work, as a proof‐of‐concept, a pH‐responsive photothermal nanoconjugate for enhanced PTT efficacy, in which graphene oxide (GO) with broad NIR absorbance and effective photothermal conversion efficiency is selected as a typical model receptor of fluorescence resonance energy transfer (FRET), and grafted cyanine dye (e.g., Cypate) acts as the donor of near‐infrared fluorescence (NIRF), is reported for the first time. The conjugate of Cypate‐grafted GO exhibits different conformations in aqueous solutions at various pH, which can trigger pH‐dependent FRET effect between GO and Cypate and thus induce pH‐responsive photothermal effect of GO‐Cypate. GO‐Cypate exhibits severe cell damage owing to the enhanced photothermal effect in lysosomes, and thus generate synergistic PTT efficacy with tumor ablation upon photoirradiation after a single‐dose intravenous injection. The photothermal nanoconjugate with broad NIR absorbance as the effective receptor of FRET can smartly convert emitted NIRF energy from donor cyanine dye into additional photothermal effect for improving PTT. These results suggest that the smart nanoconjugate can act as a promising stimuli‐responsive photothermal nanoplatform for cancer therapy.     

All‐in‐One Phototheranostics: Single Laser Triggers NIR‐II Fluorescence/Photoacoustic Imaging Guided Photothermal/Photodynamic/Chemo Combination Therapy

Development of single near‐infrared (NIR) laser triggered phototheranostics for multimodal imaging guided combination therapy is highly desirable but is still a big challenge. Herein, a novel small‐molecule dye DPP‐BT is designed and synthesized, which shows strong absorption in the first NIR window (NIR‐I) and fluorescence emission in the second NIR region (NIR‐II). Such a dye not only acts as a dual‐modal contrast agent for NIR‐II fluorescence and photoacoustic (PA) imaging, but also serves as a combined therapeutic agent for photothermal therapy (PTT) and photodynamic therapy (PDT). The single NIR laser triggered all‐in‐one phototheranostic nanoparticles are constructed by encapsulating the dye DPP‐BT, chemotherapy drug DOX, and natural phase‐change materials with a folic acid functionalized amphiphile. Notably, under NIR laser irradiation, DOX can effectively release from such nanoparticles via NIR‐induced hyperthermia of DPP‐BT. By intravenous injection of such nanoparticles into Hela tumor‐bearing mice, the tumor size and location can be accurately observed via NIR‐II fluorescence/PA dual‐modal imaging. From in vitro and in vivo therapy results, such nanoparticles simultaneously present remarkable antitumor efficacy by PTT/PDT/chemo combination therapy, which is triggered by a single NIR laser. Overall, this work provides an innovative strategy to design and construct all‐in‐one nanoplatforms for clinical phototheranostics.     

Multifunctional Au‐Coated TiO2 Nanotube Arrays as Recyclable SERS Substrates for Multifold Organic Pollutants Detection

A multifunctional Au‐coated TiO₂ nanotube array is made via synthesis of a TiO₂ nanotube array through a ZnO template, followed by deposition of Au particles onto the TiO₂ surface using photocatalytic deposition and a hydrothermal method, respectively. Such arrays exhibit superior detection sensitivity with high reproducibility and stability. In addition, due to possessing stable catalytic properties, the arrays can clean themselves by photocatalytic degradation of target molecules adsorbed to the substrate under irradiation with UV light into inorganic small molecules using surface‐enhanced Raman spectroscopy (SERS) detection, so that recycling can be achieved. Finally, by detection of Rhodamine 6G (R6G) dye, herbicide 4‐chlorophenol (4‐CP), persistent organic pollutant (POP) dichlorophenoxyacetic acid (2,4‐D), and organophosphate pesticide methyl‐parathion (MP), the unique recyclable properties indicate a new route in eliminating the single‐use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants.     

Enhanced Antitumor Efficacy by 808 nm Laser‐Induced Synergistic Photothermal and Photodynamic Therapy Based on a Indocyanine‐Green‐Attached W18O49 Nanostructure

A novel nanoplatform based on tungsten oxide (W₁₈O₄₉, WO) and indocyanine green (ICG) for dual‐modal photothermal therapy (PTT) and photodynamic therapy (PDT) has been successfully constructed. In this design, the hierarchical unique nanorod‐bundled W₁₈O₄₉ nanostructures play roles in being not only as an efficient photothermal agent for PTT but also as a potential nanovehicle for ICG molecules via electrostatic adsorption after modified with trimethylammonium groups on their surface. It is found that the ability of ICG to produce cytotoxic reactive oxygen species for PDT is well maintained after being attached on the WO, thus the as‐obtained WO@ICG can achieve a synergistic effect of combined PTT and PDT under single 808 nm near‐infrared (NIR) laser excitation. Notably, compared with PTT or PDT alone, the enhanced HeLa cells lethality of the 808 nm laser triggered dual‐modal therapy is observed. The in vivo animal experiments have shown that WO@ICG has effective solid tumor ablation effect with 808 nm NIR light irradiation, revealing the potential of these nanocomposites as a NIR‐mediated dual‐modal therapeutic platform for cancer treatment.     

Antitumor Platelet‐Mimicking Magnetic Nanoparticles

Nanoparticles possess the potential to revolutionize cancer diagnosis and therapy. The ideal theranostic nanoplatform should own long system circulation and active cancer targeting. Additionally, it should be nontoxic and invisible to the immune system. Here, the authors fabricate an all‐in‐one nanoplatform possessed with these properties for personalized cancer theranostics. Platelet‐derived vesicles (PLT‐vesicles) along with their membrane proteins are collected from mice blood and then coated onto Fe₃O₄ magnetic nanoparticles (MNs). The resulting core–shell PLT‐MNs, which inherit the long circulation and cancer targeting capabilities from the PLT membrane shell and the magnetic and optical absorption properties from the MN core, are finally injected back into the donor mice for enhanced tumor magnetic resonance imaging (MRI) and photothermal therapy (PTT). Meanwhile, it is found that the PTT treatment impels PLT‐MNs targeting to the PTT sites (i.e., tumor sites), and exactly, in turn, the enhanced targeting of PLT‐MNs to tumor sites can improve the PTT effects. In addition, since the PLT membrane coating is obtained from the mice and finally injected into the same mice, PLT‐MNs exhibit stellar immune compatibility. The work presented here provides a new angle on the design of biomimetic nanoparticles for personalized diagnosis and therapy of various diseases.     

Densely Packed Arrays of Ultra‐High‐Aspect‐Ratio Silicon Nanowires Fabricated using Block‐Copolymer Lithography and Metal‐Assisted Etching

Metal‐assisted etching is used in conjunction with block‐copolymer lithography to create ordered and densely‐packed arrays of high‐aspect‐ratio single‐crystal silicon nanowires with uniform crystallographic orientations. Nanowires with diameters and spacings down to 19 nm and 10 nm, respectively, are created as either continuous carpets or as carpets within trenches. Wires with aspect ratios up to 220 are fabricated, and capillary‐induced clustering of wires is eliminated through post‐etching critical point drying. The wires are single crystals with 〈100〉 axis directions. The distribution of wire diameters is narrow and closely follows the size distribution of the block copolymer, with a standard deviation of 3.12 nm for wires of mean diameters 22.06 nm. Wire arrays formed in carpets and in channels have hexagonal order with good fidelity to the block copolymer pattern. Fabrication of wires in topographic features demonstrates the ability to accurately control wire placement. Wire arrays made using this new process will have applications in the creation of arrays of photonic and sensing devices.     

Synthesis of Optical‐Quality Single‐Crystal β‐BaB2O4 Microwires and Nanowires

The synthesis of optical quality β‐barium borate microwires and nanowires (MNWs) is reported using an organic‐free hydrothermal method with BaCl₂·6H₂O, NaOH, and H₃BO₃ as source materials, and assisted with post‐annealing. As‐synthesized MNWs, with diameters ranging from 500 nm to 2 μm and lengths up to several hundred micrometers, show good optical‐waveguiding capabilities. Based on evanescent coupling between a single BBO MNW waveguide and a fiber taper, propagation losses of 0.30 dB μm^?1 (at 532 nm) and 0.21 dB μm^?1 (at 671 nm) are evaluated, respectively. An evident second‐harmonic generation (SHG) signal at 532 nm with a measured conversion efficiency of about 8.4% is observed when excited by waveguided 1064 nm, picosecond laser pulses within a BBO MNW with a length of the order of 100 μm. The dependence of the SHG conversion efficiency on the MNW diameter is also investigated. These results show a much‐higher SHG efficiency for BBO single‐crystal MNWs compared with bulk crystal, which suggests potential applications in future micro‐/nanoscale nonlinear optical applications such as optical modulation and frequency conversion.     

Nano Molecular‐Platform: A Protocol to Write Energy Transmission Program Inside a Molecule for Bio‐Inspired Supramolecular Engineering

In a coded self‐assembly, a simple code is written in the molecule, which self‐assembles the molecules into a fractal like structure, which acts as a seed for the next step. As the molecule turns into a complex seed, the code transforms into another form and several seeds self‐assemble into another structure, which acts as a seed for the next step. Until now, this technology was considered as a prerogative of nature. Here, a dendritic network is used to write a basic code by synthetically attaching 32 molecular rotors and doping two controller molecules in its cavity. The code live, which is an energy transmission path in the molecule, is imaged. When the energy transmission path or code is triggered, a series of products generate one after another spontaneously. Two examples are: i) dendritic seed (5–6 nm)→paired nanowire (≈12 nm)→nanowire (≈200 nm)→microwire (500 nm)→wire like rod (1–2 μm)→jelly→rectangular sheet (5 μm). ii) dendritic seed→nano‐sphere (20 nm)→micro‐sphere (500 nm)→large balls(1 μm)→oval shape rod (5–10 μm)→Y, L or T shaped rod assembly. The energy level interactions are tracked using spectroscopy how exactly a directed energy transfer code generates multi‐step synthesis from nano to the visible scale.     

10 Gbps Optical Signal Transmission via Long‐Range Surface Plasmon Polariton Waveguide

We demonstrate 10 Gbps optical signal transmission via long‐range surface plasmon polaritons (LR‐SPPs) in a very thin metal strip‐guided geometry. The LR‐SPP waveguide was fabricated as a 14 nm thick, 2.5 μm wide, and 4 cm long gold strip embedded in a polymer and pigtailed with single‐mode fibers. The total insertion loss of 16 dB was achieved at a wavelength of 1.55 μm as a carrier wave. In a 10 Gbps optical signal transmission experiment, the LR‐SPP waveguide exhibits an excellent eye opening and a 2.2 dB power penalty at 10^?12 bit error rate. We confirm, for the first time, that LR‐SPPs can efficiently transfer data signals as well as the carrier light.