Solution fabrication and photoelectrical properties of CuInS₂ nanocrystals on TiO₂ nanorod array

One-dimensional semiconductor architectures are receiving attention in preparing photovoltaic solar cells because of its superior charge transport as well as excellent light-harvesting efficiency. In this study, vertically aligned single-crystalline TiO(2) nanorods array was grown directly on transparent conductive glass (FTO), and then CuInS(2) nanocrystals were deposited on nanorods array by spin coating method to form TiO(2)/CuInS(2) heterostructure films. The resulting nanostructure assembly and composition was confirmed by field-emission scanning electron microscope (FESEM) , transmission electron microscopy (TEM), high-resolution TEM, and X-ray diffraction(XRD). Ultraviolet-visible absorption spectroscopy (UV-vis) data indicates that the absorbance of the nanocomposite film extended into the visible region compared with bare TiO(2) nanorod arrays. The surface photovoltage spectra (SPS) also showed a new and enhanced response region corresponding to the absorption spectrum. These results suggest that the novel CuInS(2) nanocrystals sensitized TiO(2) nanorod array on FTO photoelectrodes has a potential application in photovoltaic devices.     

Fabrication of 3D interconnected porous TiO2 nanotubes templated by poly(vinyl chloride-g-4-vinyl pyridine) for dye-sensitized solar cells

Porous TiO(2) nanotube arrays with three-dimensional (3D) interconnectivity were prepared using a sol-gel process assisted by poly(vinyl chloride-graft-4-vinyl pyridine), PVC-g-P4VP graft copolymer and a ZnO nanorod template. A 7 μm long ZnO nanorod array was grown from the fluorine-doped tin oxide (FTO) glass via a liquid phase deposition method. The TiO(2) sol-gel solution templated by the PVC-g-P4VP graft copolymer produced a random 3D interconnection between the adjacent ZnO nanorods during spin coating. Upon etching of ZnO, TiO(2) nanotubes consisting of 10-15 nm nanoparticles were generated, as confirmed by wide-angle x-ray scattering (WAXS), energy-filtering transmission electron microscopy (EF-TEM) and field-emission scanning electron microscopy (FE-SEM). The ordered and interconnected nanotube architecture showed an enhanced light scattering effect and increased penetration of polymer electrolytes in dye-sensitized solar cells (DSSC). The energy conversion efficiency reached 1.82% for liquid electrolyte, and 1.46% for low molecular weight (M(w)) and 0.74% for high M(w) polymer electrolytes.     

Aptamer-enabled efficient isolation of cancer cells from whole blood using a microfluidic device

Circulating tumor cells (CTC) in the peripheral blood could provide important information for diagnosis of cancer metastasis and monitoring treatment progress. However, CTC are extremely rare in the bloodstream, making their detection and characterization technically challenging. We report here the development of an aptamer-mediated, micropillar-based microfluidic device that is able to efficiently isolate tumor cells from unprocessed whole blood. High-affinity aptamers were used as an alternative to antibodies for cancer cell isolation. The microscope-slide-sized device consists of >59,000 micropillars, which enhanced the probability of the interactions between aptamers and target cancer cells. The device geometry and the flow rate were investigated and optimized by studying their effects on the isolation of target leukemia cells from a cell mixture. The device yielded a capture efficiency of ~95% with purity of ~81% at the optimum flow rate of 600 nL/s. Further, we exploited the device for isolating colorectal tumor cells from unprocessed whole blood; as few as 10 tumor cells were captured from 1 mL of whole blood. We also addressed the question of low throughput of a typical microfluidic device by processing 1 mL of blood within 28 min. In addition, we found that ~93% of the captured cells were viable, making them suitable for subsequent molecular and cellular studies.     

Controllable growth of highly ordered ZnO nanorod arrays via inverted self-assembled monolayer template

This article presents a facile and effective approach to the controllable growth of highly ordered and vertically aligned ZnO nanorod arrays on the GaN substrate via a hydrothermal route by using the TiO(2) ring template deriving from the polystyrene microsphere self-assembled monolayer. The size of TiO(2) ring template can be flexibly tuned from 50 to 400 nm for the 500 nm polystyrene microspheres by varying the time of reactive ion etching and the concentration of TiO(2) sol. As a result, the diameter of the individual ZnO nanorods can be potentially tuned over a wide range. The combination of several characterization techniques has demonstrated that the ordered ZnO nanorods are highly uniform in diameter and height with perfect alignment and are epitaxially grown along [0001] direction. This work provides a novel and accessible route to prepare oriented and aligned ZnO nanorod arrays with high crystalline quality.     

TiO2 nanorod arrays functionalized with In2S3 shell layer by a low-cost route for solar energy conversion

We report the fabrication and characterization of a TiO(2)-In(2)S(3) core-shell nanorod array structure for application of semiconductor-sensitized solar cells. Hydrothermally synthesized TiO(2) nanorod arrays on FTO glass substrates are functionalized with a uniform In(2)S(3) shell layer by using the successive ion layer adsorption and reaction (SILAR) method. This low-cost technique promotes a uniform deposition of In(2)S(3) nanoshells on the surface of TiO(2) nanorods, thus forming an intact interface between the In(2)S(3) shell and TiO(2) core. Results show that the thickness of In(2)S(3) shell layers as well as the visible light absorption threshold can be effectively controlled by varying the coating cycles during the SILAR process. The best reproducible performance of the sandwich solar cell using the TiO(2)-In(2)S(3) core-shell nanorod arrays as photoelectrodes was obtained after 30 SILAR cycles, exhibiting a short-circuit current (I(sc)) of 2.40 mA cm(-2), an open-circuit voltage (V(oc)) of 0.56 V, a fill factor (ff) of 0.40 and a conversion efficiency (η) of 0.54%, respectively. These results demonstrate a feasible and controllable route towards In(2)S(3) coating on a highly structured substrate and a proof of concept that such TiO(2)-In(2)S(3) core-shell architectures are novel and promising photoelectrodes in nanostructured solar cells.     

Branched TiO₂ nanorods for photoelectrochemical hydrogen production

We report a hierarchically branched TiO(2) nanorod structure that serves as a model architecture for efficient photoelectrochemical devices as it simultaneously offers a large contact area with the electrolyte, excellent light-trapping characteristics, and a highly conductive pathway for charge carrier collection. Under Xenon lamp illumination (UV spectrum matched to AM 1.5G, 88 mW/cm(2) total power density), the branched TiO(2) nanorod array produces a photocurrent density of 0.83 mA/cm(2) at 0.8 V versus reversible hydrogen electrode (RHE). The incident photon-to-current conversion efficiency reaches 67% at 380 nm with an applied bias of 0.6 V versus RHE, nearly two times higher than the bare nanorods without branches. The branches improve efficiency by means of (i) improved charge separation and transport within the branches due to their small diameters, and (ii) a 4-fold increase in surface area which facilitates the hole transfer at the TiO(2)/electrolyte interface.     

Affinity Versus Label‐Free Isolation of Circulating Tumor Cells: Who Wins?

The study of circulating tumor cells (CTCs) has been made possible by many technological advances in their isolation. Their isolation has seen many fronts, but each technology brings forth a new set of challenges to overcome. Microfluidics has been a key player in the capture of CTCs and their downstream analysis, with the aim of shedding light into their clinical application in cancer and metastasis. Researchers have taken diverging paths to isolate such cells from blood, ranging from affinity‐based isolation targeting surface antigens expressed on CTCs, to label‐free isolation taking advantage of the size differences between CTCs and other blood cells. For both major groups, many microfluidic technologies have reported high sensitivity and specificity for capturing CTCs. However, the question remains as to the superiority among these two isolation techniques, specifically to identify different CTC populations. This review highlights the key aspects of affinity and label‐free microfluidic CTC technologies, and discusses which of these two would be the highest benefactor for the study of CTCs.     

新型Sb2S3-Sb2Se3与单晶二氧化钛纳米阵列复合结构在太阳能电池领域的应用

近年来,半导体量子点敏化太阳能电池作为新一代的太阳能电池,引起了广泛的关注．Sb2S2和Sb2Se3量子点由于具有出色的光吸收特性与带隙的可调控性,已成为敏化太阳能电池领域的重要组成部分．通过水热法,二氧化钛（TiO2）单晶纳米阵列被成功生长在FTO导电玻璃上．通过连续离子层吸附法（SILAR）,Sb2S3Sb2Se3复合纳米结构被生长在二氧化钛单晶纳米阵列的表面．利用x射线衍射（XRD）表征Sb2S3和Sb2Se3纳米晶体的晶相,利用扫描电子显微镜（SEM）表征其形貌,发现在这一复合结构中,二氧化钛单晶纳米阵列与Sb2S3结合之后所留下的空隙被Sb2Se3量子点填充,从而提高了结构表面积的利用率．随着连续离子层吸附法反应周期的增加,Sb2S3-Sb2Se3,与二氧化钛单晶纳米阵列共同形成复合结构的带隙发生了明显的红移,吸收边在可调控的情况下由1．7eV向红外波段发生了移动．这种纳米结构的比表面积大、工艺简单、结构致密、沉积速率快、可调控性强,对于今后敏化太阳能电池领域的应用有很大的启发作用．     

A Radial Flow Microfluidic Device for Ultra‐High‐Throughput Affinity‐Based Isolation of Circulating Tumor Cells

Circulating tumor cells (CTCs) are believed to play an important role in metastasis, a process responsible for the majority of cancer‐related deaths. But their rarity in the bloodstream makes microfluidic isolation complex and time‐consuming. Additionally the low processing speeds can be a hindrance to obtaining higher yields of CTCs, limiting their potential use as biomarkers for early diagnosis. Here, a high throughput microfluidic technology, the OncoBean Chip, is reported. It employs radial flow that introduces a varying shear profile across the device, enabling efficient cell capture by affinity at high flow rates. The recovery from whole blood is validated with cancer cell lines H1650 and MCF7, achieving a mean efficiency >80% at a throughput of 10 mL h^?1 in contrast to a flow rate of 1 mL h^?1 standardly reported with other microfluidic devices. Cells are recovered with a viability rate of 93% at these high speeds, increasing the ability to use captured CTCs for downstream analysis. Broad clinical application is demonstrated using comparable flow rates from blood specimens obtained from breast, pancreatic, and lung cancer patients. Comparable CTC numbers are recovered in all the samples at the two flow rates, demonstrating the ability of the technology to perform at high throughputs.     

High efficiency dye-sensitized solar cells based on hierarchically structured nanotubes

Dye-sensitized solar cells (DSSCs) based on hierarchically structured TiO(2) nanotubes prepared by a facile combination of two-step electrochemical anodization with a hydrothermal process exhibited remarkable performance. Vertically oriented, smooth TiO(2) nanotube arrays fabricated by a two-step anodic oxidation were subjected to hydrothermal treatment, thereby creating advantageous roughness on the TiO(2) nanotube surface (i.e., forming hierarchically structured nanotube arrays-nanoscopic tubes composed of a large number of nanoparticles on the surface) that led to an increased dye loading. Subsequently, these nanotubes were exploited to produce DSSCs in a backside illumination mode, yielding a significantly high power conversion efficiency, of 7.12%, which was further increased to 7.75% upon exposure to O(2) plasma.     

Microchip device with 64-site electrode array for multiplexed immunoassay of cell surface antigens based on electrochemiluminescence resonance energy transfer

This paper describes a novel on-chip microarray platform based on an electrochemiluminescence resonance energy transfer (ECL-RET) strategy for rapid assay of cancer cell surface biomarkers. This platform consists of 64 antigen-decorated CdS nanorod spots with the diameter of 1.0 cm uniformly distributed on 16 indium tin oxide (ITO) strips, which is coated with a multichannel decorated polydimethylsiloxane (PDMS) slice to realize multiplexed determination of antigens. To shorten the immune reaction time in the microchannels and simplify the device, magnetic stirring and four-channel universal serial bus (USB) ports for plug-and-play were used. When Ru(bpy)(3)(2+) labeled antibodies were selectively captured by the corresponding antigens on the CdS nanorod spot array, ECL-RET from the CdS nanorod (donor) by cathodic emission in the presence of K(2)S(2)O(8) to Ru(bpy)(3)(2+) (acceptor) occurred. With signal amplification of Ru(bpy)(3)(2+) and competitive immunoassay, carcinoembryonic antigen (CEA), α-fetoprotein (AFP), and prostate specific antigen (PSA) as models were detected on this microfluidic device via recording the increased ECL-RET signals on electrode surfaces. Furthermore, this multiplexed competitive immunoassay was successfully used for detecting cancer cell surface antigens via the specific antibody-cell interactions and cell counting via cell surface receptors and antigens on the CdS nanorod surface. This platform provides a rapid and simple but sensitive approach with microliter-level sample volume and holds great promise for multiplexed detection of antigens and antigen-specific cells.     

Effect of highly ordered single-crystalline TiO2 nanowire length on the photovoltaic performance of dye-sensitized solar cells

One-dimensional semiconductor nanostructures grown directly onto transparent conducting oxide substrates with a high internal surface area are most desirable for high-efficiency dye-sensitized solar cells (DSSCs). Herein, we present a multicycle hydrothermal synthesis process to produce vertically aligned, single crystal rutile TiO(2) nanowires with different lengths between 1 and 8 μm for application as the working electrode in DSSCs. Optimum performance was obtained with a TiO(2) nanowire length of 2.0 μm, which may be ascribed to a smaller nanowire diameter with a high internal surface area and better optical transmittance with an increase in the incident light intensity on the N719 dye; as well as a firm connection at the FTO/TiO(2) nanowire interface.     

Hydrothermal synthesis of anatase TiO2 nanorods with high crystallinity using ammonia solution as a solvent

Anatase TiO2 nanorods with high crystallinity were synthesized using ammonia solution (28%) as a solvent by through the hydrothermal method. The X-ray diffraction pattern confirmed the product's anatase phase and high crystallinity, and the transmission electron microscope (TEM) image demonstrated the unique morphologies of the two ends of the TiO2 nanorods (two tringle-horn shapes and one round-horn shape), whose lengths and widths were within the ranges of 200-300 and 60-110 nm, respectively. The high-resolution TEM image clearly displayed the crystal lattices of the (101) planes lying along the direction of the lengthes of the TiO2 nanorods. The energy dispersive X-ray spectrum of a TiO2 nanorod revealed the presence of about 4 atm% nitrogen element as a trace in the anatase TiO2 nanorod. The Raman spectrum of the TiO2 nanorods also showed the typical bands of anatase TiO2 and very weak peaks resulting from the TiN first-order defect-induced Raman scattering. The UV-vis diffuse-reflectance spectra showed a slight red shift (about 3 nm) of the anatase TiO2 nanorods compared with P25, which probably resulted from the trace of TiN on the surfaces of the anatase TiO2 nanorods. A three-stage-process mechanism model is proposed for the formation of the nanorods: Rhombus crystallites bounded by four {101} faces are first formed through anisotropic growth, then longer rhombus crystallites are grown via oriented attachment, finally, nanorods with a unique morphology are self-assembled by Van Der Waals forces.     

Channel surface patterning of alternating biomimetic protein combinations for enhanced microfluidic tumor cell isolation

Here, we report a new method for multicomponent protein patterning in a microchannel and also a technique for improving immunoaffinity-based circulating tumor cell (CTC) capture by patterning regions of alternating adhesive proteins using the new method. The first of two proteins, antiepithelial cell adhesion molecule (anti-EpCAM), provides the specificity for CTC capture. The second, E-selectin, increases CTC capture under shear. Patterning regions with and without E-selectin allows captured leukocytes, which also bind E-selectin and are unwanted impurities in CTC isolation, to roll a short distance and detach from the capture surface. This reduces leukocyte capture by up to 82%. The patterning is combined with a leukocyte elution step in which a calcium chelating buffer effectively deactivates E-selectin so that leukocytes may be rinsed away 60% more efficiently than with a buffer containing calcium. The alternating patterning of this biomimetic protein combination, used in conjunction with the elution step, reduces capture of leukocytes while maintaining a high tumor cell capture efficiency that is up to 1.9 times higher than the tumor cell capture efficiency of a surface with only anti-EpCAM. The new patterning technique described here does not require mask alignment and can be used to spatially control the immobilization of any two proteins or protein mixtures inside a sealed microfluidic channel.     

Nanostructured nanorod arrays presenting TiO2 nanorods/poly(3-hexylthiophene) for solar cells application

We have fabricated inverted heterojunction solar cell devices incorporating titanium dioxide nanorod/poly(3-hexylthiophene) (P3HT) rod arrays using melt-assisted anodic alumina oxide template. Using transmission electron microscopy and conductance atomic force microscopy, we revealed that phase-separated TiO2 rich (n-type) and P3HT rich (p-type) regions presents in these rod arrays. The optimized composite rod array structure had a higher hole mobility than that of the blend film consisting of TiO2 nanorod and P3HT as determined by fitting the dark J-V curves into the space charge-limited current model. The more efficient carrier transport of the device incorporating the nanorod arrays provided it with both a higher short-circuit current density and power conversion efficiency.     

Selective formation of GaN-based nanorod heterostructures on soda-lime glass substrates by a local heating method

We report on the fabrication of high-quality GaN on soda-lime glass substrates, heretofore precluded by both the intolerance of soda-lime glass to the high temperatures required for III-nitride growth and the lack of an epitaxial relationship with amorphous glass. The difficulties were circumvented by heteroepitaxial coating of GaN on ZnO nanorods via a local microheating method. Metal-organic chemical vapor deposition of ZnO nanorods and GaN layers using the microheater arrays produced high-quality GaN/ZnO coaxial nanorod heterostructures at only the desired regions on the soda-lime glass substrates. High-resolution transmission electron microscopy examination of the coaxial nanorod heterostructures indicated the formation of an abrupt, semicoherent interface. Photoluminescence and cathodoluminescence spectroscopy was also applied to confirm the high optical quality of the coaxial nanorod heterostructures. Mg-doped GaN/ZnO coaxial nanorod heterostructure arrays, whose GaN shell layers were grown with various different magnesocene flow rates, were further investigated by using photoluminescence spectroscopy for the p-type doping characteristics. The suggested method for fabrication of III-nitrides on glass substrates signifies potentials for low-cost and large-size optoelectronic device applications.     

Freezing a water droplet on an aligned Si nanorod array substrate

When a water droplet is dried on a vertically aligned Si nanorod array surface, the nanorods are bundled together. To understand how bundles are formed, a water droplet is frozen rapidly on a Si nanorod array surface observed under a cryo-SEM (scanning electron microscope). The nanorods in the precursor film form similar bundles as those dried in air. But the nanorods under the apparent frozen water droplet are only slightly deformed. We propose that the bundling of nanorods is caused by non-uniform water-nanorod interaction, which could happen either during the water spreading or drying process. Therefore, controlling the liquid-nanostructure interaction could minimize the bundling. In addition, the rapid freezing process does not preserve the water inside the nanochannels, and almost all the water forms ice on top of the nanorod surface, either as a planar interface or as particles, depending on the locations. The separated ice-nanorod interface will have potential applications in chemical separation and crystal growth.     

Negative enrichment of target cells by microfluidic affinity chromatography

A three-dimensional microfluidic channel was developed for high-purity cell separations. This system featured high capture affinity using multiple vertical inlets to an affinity surface. In cell separations, positive selection (capture of the target cell) is usually employed. Negative enrichment, the capture of nontarget cells and elution of target cells, has distinct advantages over positive selection. In negative enrichment, target cells are not labeled and are not subjected to strenuous elution conditions or dilution. As a result, negative enrichment systems are amenable to multistep processes in microfluidic systems. In previous work (Li, P.; Tian, Y.; Pappas, D. Anal. Chem.2011, 83, 774-781), we reported cell capture enhancement effects at vertical inlets to the affinity surface. In this study, we designed a chip that has multiple vertical and horizontal channels, forming a three-dimensional separation system. Enrichment of target cells showed separation purities of 92-96%, compared with straight-channel systems (77% purity). A parallelized chip was also developed for increased sample throughput. A two-channel system showed similar separation purity with twice the sample flow rate. This microfluidic system, featuring high separation purity and ease of fabrication and use is suitable for cell separations when subsequent analysis of target cells is required.     

Mesocrystalline TiO<Subscript>2</Subscript> nanosheet arrays with exposed {001} facets: Synthesis via topotactic transformation and applications in dye-sensitized solar cells

A facile,fluorine-free approach for synthesizing vertically aligned arrays of mesocrystalline anatase TiO2 nanosheets with highly exposed {001} facets was developed through topotactic transformation.Unique mesocrystalline {001}-faceted TiO2 nanosheet arrays vertically aligned on conductive fluorine-doped tin oxide glass were realized through topotactic conversion from single-crystalline precursor nanosheet arrays based on lattice matching between the precursor and the anatase crystals.The morphology and microstructure of the {001}-faceted TiO2 nanosheets could be readily modulated by changing the reactant concentration and annealing temperature.Owing to enhanced dye adsorption,reduced charge recombination,and enhanced light scattering arising from the exposed {001} facets,in addition to the advantageous features of low-dimensional structure arrays (e.g.,fast electron transport and efficient charge collection),the obtained TiO2 nanosheet arrays exhibited superior performance when they were used as anodes for dye-sensitized solar cells (DSSCs).Particularly,{001}-faceted TiO2 nanosheet arrays ～15 μm long annealed at 500 ℃ showed a power conversion efficiency of 7.51％.Furthermore,a remarkable efficiency of 8.85％ was achieved for a DSSC based on double-layered TiO2 nanosheet arrays ～35 μm long,which were prepared by conversion from the precursor nanoarrays produced via secondary hydrothermal growth.     

CeO2修饰的透明TiO2纳米管电极的电致变色器件

采用电化学沉积法在阳极氧化制备的TiO2纳米管阵列管壁上沉积一层CeO2纳米颗粒,再将CeO2修饰的透明TiO2纳米管阵列薄膜对电极与聚三甲基噻吩变色电极组装成透过型电致变色器件.实验结果表明:CeO2修饰的TiO2纳米管阵列薄膜仍保持良好的光透过性,其电荷存储能力比纯TiO2纳米管电极提高了30%.经CeO2修饰的TiO2纳米管改善了器件的性能,与对电极为单一TiO2纳米管阵列的器件相比,其对比度仍保持在38%左右,其褪色时间由1.3 s缩短为0.8 s.电致变色器件快速响应得益于纳米管与纳米颗粒组成的复合结构的高比表面积和快速的电荷传输过程.