Synthesis of W18O49 nanorod via ammonium tungsten oxide and its interesting optical properties

W(18)O(49) nanorods were synthesized by pyrolyzing (NH(4))(x)WO(3+x/2) nanorods precursors, which were prepared by a hydrothermal reaction using sulfate as a structure-directing agent, in a reductive atmosphere of H(2)(5 vol %)/N(2) at 500 °C for 1 h. W(18)O(49) nanorods showed high transmittance in the visible region as well as excellent shielding properties of NIR lights. A simulated experiment revealed that excellent heat insulating performance can be realized by applying a 70% visible light transparent W(18)O(49) coating on a quartz glass. Meanwhile, the W(18)O(49) nanorods also showed strong absorption of NIR light and instantaneous conversion of photoenergy to heat. In a word, W(18)O(49) nanorods hold interesting optical properties and are a promising material in a wide range of applications.     

Promoting infrared light driven photocatalytic activity of W18O49 nanorods by coupling polypyrrole

Research on Chemical Intermediates - It is essential to promote the infrared light driven photocatalytic activity of W18O49. To do this, W18O49 nanorods coupled with polypyrrole (PPY) have been...     

Synthesis of WO3 nanorods by reacting WO(OMe)4 under autogenic pressure at elevated temperature followed by annealing

This article reports on the fabrication of WO(3) nanorods using an efficient straightforward synthetic technique, without a catalyst, and using a single precursor. The thermal dissociation of WO(OMe)(4) at 700 degrees C in a closed Swagelok cell under an air/inert atmosphere yielded W(18)O(49) nanorods. Annealing of W(18)O(49) at 500 degrees C under an air atmosphere led to the formation of pure WO(3) nanorods. The obtained products are characterized by morphological (scanning electron microscopy and transmission electron microscopy), structural (X-ray diffraction analysis, high-resolution scanning electron microscopy, and Raman spectroscopy), and compositional [energy-dispersive X-ray and elemental (C, H, N, S) analysis] measurements. The mechanism of the formation of nonstoichiometric W(18)O(49) nanorods is supported by the measured analytical data and several control experiments.     

Novel route to WOx nanorods and WS2 nanotubes from WS2 inorganic fullerenes

WO(x) (2 < x < 3) and WS(2) nanostructures have been widely praised due to applications as catalysts, solid lubricants, field emitters, and optical components. Many methods have been developed to fabricate these nanomaterials; however, most attention was focused on the same dimensional transformation from WO(x) nanoparticles or nanorods to WS(2) nanoparticles or nanotubes. In a solid-vapor reaction, by simply controlling the quantity of water vapor and reaction temperature, we have realized the transformation from quasi-zero-dimensional WS(2) nanoparticles to one-dimensional W(18)O(49) nanorods, and subsequent sulfuration reactions have further converted these W(18)O(49) nanorods into WS(2) nanotubes. The reaction temperature, quantity of water vapor, and pretreatment of the WS(2) nanoparticle precursors are important process parameters for long, thin, and homogeneous W(18)O(49) nanorods growth. The morphologies, crystal structures, and circling transformation mechanisms of sulfide-oxide-sulfide are discussed, and the photoluminescence properties of the resulting nanorods are investigated using a Xe lamp under an excitation of 270 nm.     

An inorganic route for controlled synthesis of W18O49 nanorods and nanofibers in solution

In this work, we describe a simple inorganic route for synthesis of monodispersed W(18)O(49) nanorods with dimensional control in the quantum confinement regime. The single-crystalline W(18)O(49) nanorods can be prepared into stable colloidal solutions, or assembled into fibrous and/or paper forms by tuning process parameters. The important role of Na(2)SO(4) salt in the synthesis has been demonstrated. This inorganic route should be feasible for large-scale production of low-dimensional nanostructured W(18)O(49).     

热电子驱动氧化钨/石墨化氮化碳S-型异质结实现宽光谱光催化产氢活性

近年来,等离子体材料因具有独特的局域表面等离子体共振(LSPR)效应,可实现可见光到近红外范围内光利用,因此引起人们的广泛关注.利用等离子体材料(贵金属或重掺杂半导体材料)合理构建异质结构,可以同时拓宽光催化剂的光谱响应范围,抑制载流子的复合,从而提高光催化活性.在已报道的等离子体半导体中,WO3–x具有无毒、价廉以及光谱响应宽等优异特性.本文通过将一维等离子体W18O49纳米线负载到2D g-C3N4纳米片上,构建了WO3–x/HCN S型异质结光催化剂.在可见光下光催化产氢活性测试中,纯相质子化氮化碳(HCN)的产氢活性相对较低,为259μmol·g?1·h?1,而W18O49/HCN复合材料的产氢活性显著高于HCN,其中性能最优的W18O49/HCN复合材料产氢速率为892μmol·g?1·h?1,约为HCN的3.4倍.在550 nm单色光照射下,W18O49/HCN复合材料的产氢速率仍有41.5μmol·g?1·h?1,纯相HCN和W18O49均未有H2生成.在420,450,520 nm处测得的W18O49/HCN复合材料的表观量子效率分别为6.21％,1.28％和0.14％.W18O49纳米线起着扩展光吸附和热电子供体的双重作用,使WO3–x/g-C3N4具有宽光谱响应的光催化分解水活性.等离子体W18O49纳米线可以产生热电子,热电子转移到HCN的导带(CB),参与水还原反应,实现宽光谱的光催化产氢活性.利用固体紫外测试确定了W18O49/HCN复合材料能带结构,与传统的WO3催化剂相比,W18O49在500–1200 nm处表现出明显的尾部吸收,这是由于W18O49大量的氧空位引起的LSPR效应.而W18O49/HCN异质结具有比HCN更长的吸收边.通过第一原理密度泛函理论模拟计算了W18O49和HCN的功函数,分别为5.73和3.95 eV.因此,当HCN与W18O49结合形成紧密的界面时,电子会从做功函数小的HCN向做功函数大的W18O49移动,直至达到费米能级平衡,形成内建电场.此外,由于电子数量的减少,HCN的能带边缘向上弯曲,而由于电子的捕获,W18O49能带边缘向下弯曲,这种向上与向下的能带弯曲是S型结构的典型特征之一,这也与XPS测试结果相吻合.W18O49/HCN异质结内建电场驱动WO3–x中导带(CB)的电子向g-C3N4的价带(VB)移动.在该设计中,效率低的电子和空穴被重新组合并排出,而具有高氧化还原能力的功能电子和空穴则被保留下来.不仅如此,S-scheme有望同时引导光生电子和热电子运动,从而避免逆电荷传递,有利于热电子的有效利用.W18O49和g-C3N4匹配的带隙所产生的S-scheme可以导致较强的氧化还原能力和较高的光诱导电荷迁移速率.对HCN与W18O49/HCN光电性能的测试结果表明,1D/2D W18O49/HCN异质结的构建可以充分改善光生电子-空穴对的分离和迁移,进而表现出更好的光催化活性.电子自旋共振结果也证实了W18O49/HCN中S型电荷转移机制.     

Coordinatively induced length control and photoluminescence of W18O49 nanorods

A coordinatively induced length control of W18O49 nanorods has been developed using thermal decomposition of W(CO)6 in octyl ether solutions of single or mixed capping agents, oleic acid (OA), oleic acid/hexadecylamine (HDA), and oleic acid/trioctylphosphine oxide (TOPO). The order of length for nanorods synthesized with different capping agents was OA > OA/HDA > OA/TOPO, which was the opposite of order of their coordinating power. The order of crystalline size (diameter x length) from the TEM image was OA/HDA > OA > OA/TOPO and matched exactly with the order of crystallinity from the XRD pattern. The order of photoluminescence intensity was OA/HDA < OA < OA/TOPO and was the opposite of the order for the crystalline size or crystallinity. The strong coordinating power and steric bulkiness of TOPO is thought to interrupt the growth of the nanorods, the rearrangement of the end face atoms, and the fusion of the lateral faces and, thereby, increase the oxygen defects and the photoluminescence intensity.     

无种子法纳米金棒的制备及其对肿瘤细胞光热治疗效应研究

采用简便快捷的无种子法一步完成了纳米金棒的制备.通过改变实验条件可以调控纳米金棒的吸收峰从可见到近红外转移.将巯基聚乙二醇(PEG-SH)置换金棒表面的十六烷基三甲基溴化铵(CTAB)分子,大大提高了金棒的生物相容性.制备的纳米金棒在近红外(NIR)光照射下对肿瘤细胞有很好的杀伤效果.研究结果为纳米金棒用于抗肿瘤治疗提供了实验基础.     

无种子法纳米金棒的制备及其对肿瘤细胞光热治疗效应研究

采用简便快捷的无种子法一步完成了纳米金棒的制备. 通过改变实验条件可以调控纳米金棒的吸收峰从可见到近红外转移. 将巯基聚乙二醇（PEG-SH）置换金棒表面的十六烷基三甲基溴化铵（CTAB）分子,大大提高了金棒的生物相容性. 制备的纳米金棒在近红外（NIR）光照射下对肿瘤细胞有很好的杀伤效果.研究结果为纳米金棒用于抗肿瘤治疗提供了实验基础.     

Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods

Due to strong electric fields at the surface, the absorption and scattering of electromagnetic radiation by noble metal nanoparticles are strongly enhanced. These unique properties provide the potential of designing novel optically active reagents for simultaneous molecular imaging and photothermal cancer therapy. It is desirable to use agents that are active in the near-infrared (NIR) region of the radiation spectrum to minimize the light extinction by intrinsic chromophores in native tissue. Gold nanorods with suitable aspect ratios (length divided by width) can absorb and scatter strongly in the NIR region (650-900 nm). In the present work, we provide an in vitro demonstration of gold nanorods as novel contrast agents for both molecular imaging and photothermal cancer therapy. Nanorods are synthesized and conjugated to anti-epidermal growth factor receptor (anti-EGFR) monoclonal antibodies and incubated in cell cultures with a nonmalignant epithelial cell line (HaCat) and two malignant oral epithelial cell lines (HOC 313 clone 8 and HSC 3). The anti-EGFR antibody-conjugated nanorods bind specifically to the surface of the malignant-type cells with a much higher affinity due to the overexpressed EGFR on the cytoplasmic membrane of the malignant cells. As a result of the strongly scattered red light from gold nanorods in dark field, observed using a laboratory microscope, the malignant cells are clearly visualized and diagnosed from the nonmalignant cells. It is found that, after exposure to continuous red laser at 800 nm, malignant cells require about half the laser energy to be photothermally destroyed than the nonmalignant cells. Thus, both efficient cancer cell diagnostics and selective photothermal therapy are realized at the same time.     

一维纳米材料Cs0.2WO3和W18O49长度与红外吸收关联性的Mie散射理论推导及实验验证

研究表明二元、三元钨基氧化物的红外吸收性能具有尺寸和形貌依赖性,但还没有普适性的物理学机理及计算方法。本工作基于Mie散射理论,推导了一维材料的长度与光吸收性能之间的关系,通过理论推导计算和实验验证,探究了纳米钨基氧化物的红外吸收性能与颗粒长度的关联性。首先,基于Mie散射理论的推演和计算,揭示了增加纳米Cs_(0.2)WO_3和W_(18)O_(49)材料长度可适度提高其近红外吸收性能的规律。其次,测试了合成的不同长度Cs_(0.2)WO_3纳米棒和W_(18)O_(49)纳米线的红外吸收性能,结果与理论计算及模拟相吻合。其中在2 500～20 000 nm波长范围内Cs_(0.2)WO_3纳米棒和W_(18)O_(49)纳米线随长度的变化趋势不同,Cs_(0.2)WO_3纳米棒的红外吸收性能随长度的增加而增加,而W_(18)O_(49)纳米线的红外吸收性能随长度的增加而减弱。Cs_(0.2)WO_3纳米棒和W_(18)0O_9纳米线的光热效应均随长度的增加而增加,增幅分别达18.5%和12.7%,再次验证了长度效应。     

Synthesis and characterization of PbS nanorods in W/O microemulsion system

PbS nanorods have been successfully synthesized in water-in-oil (W/O) microemulsion containing non-ionic surfactant OP, n-pentanol, cyclohexane, and aqueous solution. The effects of the molar ratio of water to surfactant (ω₀), the concentration of reactants and the ageing time on the morphologies of PbS nanoparticles were investigated. The microstructures, morphologies and properties of the synthesized products were characterized by means of X-ray diffraction, transmission electron microscopy, and ultraviolet-visible (UV-VIS) absorption spectroscopy, respectively. The results showed that the synthesized rod-like products are composed of cubic phase PbS. These nanorods have an average diameter of about 100 nm, and an average length of about 500 nm. In the UV-VIS absorption spectrum, the absorption edge of PbS nanorods exhibit a blue shift compared with that of bulk PbS, indicating the quantum confinement effect of PbS nano-particles     

A unique class of near-infrared functional fluorescent dyes with carboxylic-acid-modulated fluorescence ON/OFF switching: rational design, synthesis, optical properties, theoretical calculations, and applications for fluorescence imaging in living animals

Fluorescence imaging is one of the most powerful techniques for monitoring biomolecules in living systems. Fluorescent sensors with absorption and emission in the near-infrared (NIR) region are favorable for biological imaging applications in living animals, as NIR light leads to minimum photodamage, deep tissue penetration, and minimum background autofluorescence interference. Herein, we have introduced a new strategy to design NIR functional dyes with the carboxylic-acid-controlled fluorescence on-off switching mechanism by the spirocyclization. Based on the design strategy, we have developed a series of Changsha (CS1-6) NIR fluorophores, a unique new class of NIR functional fluorescent dyes, bearing excellent photophysical properties including large absorption extinction coefficients, high fluorescence quantum yields, high brightness, good photostability, and sufficient chemical stability. Significantly, the new CS1-6 NIR dyes are superior to the traditional rhodamine dyes with both absorption and emission in the NIR region while retaining the rhodamine-like fluorescence ON-OFF switching mechanism. In addition, we have performed quantum chemical calculations with the B3LYP exchange functional employing 6-31G* basis sets to shed light on the structure-optical properties of the new CS1-6 NIR dyes. Furthermore, using CS2 as a platform, we further constructed the novel NIR fluorescent TURN-ON sensor 7, which is capable of imaging endogenously produced HClO in the living animals, demonstrating the value of our new CS NIR functional fluorescent dyes. We expect that the design strategy may be extended for development of a wide variety of NIR functional dyes with a suitable fluorescence-controlled mechanism for many useful applications in biological studies.     

Ionic liquid-enhanced photooxidation of water using the polyoxometalate anion [P2W18O62](6-) as the sensitizer

Simple polyoxometalate anions are known to be photoreduced in molecular solvents in the presence of 2-propanol or benzyl alcohol. The use of ionic liquids (ILs) as the solvent is now reported to also allow the photooxidation of water to be achieved. In particular, the photochemistry of the classic Dawson polyoxometalate salt K(6)[P(2)W(18)O(62)] has been studied in detail when water is present in the aprotic IL, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) and the protic IL, diethanolamine hydrogen sulfate (DEAS). In these and other ILs, irradiation with white light (wavelength 275-750 nm) or UV light (wavelength 275-320 nm) leads to overall reduction of the [P(2)W(18)O(62)](6-) anion to [P(2)W(18)O(62)](7-) and concomitant oxidation of water to dioxygen and protons. The modified structure of bulk water present in ILs appears to facilitate its oxidation. Analogous results were obtained in aqueous solutions containing the protic IL as an electrolyte. The photoproducts (reduced polyoxometalate anion, dioxygen, and protons) were identified by, respectively, voltammetry, a Clark electrode, and monitoring of pH. The formal reversible potentials E(0)(F) for [P(2)W(18)O(62)](6-/7-/8-/9-/10-) couples are much more positive than in molecular solvents. The [P(2)W(18)O(62)](8-) and more reduced anions, if formed as intermediates, would efficiently reduce photoproducts H(+) or dioxygen to produce [P(2)W(18)O(62)](7-), rather than reform to [P(2)W(18)O(62)](6-). Thus, under photoirradiation conditions [P(2)W(18)O(62)](7-) acts as a kinetic sink so that in principle indirect splitting of water to produce dioxygen and dihydrogen can be achieved. The equivalent form of photooxidation does not occur in liquid water or in molecular solvents such as MeCN and MeCN/CH(2)Cl(2) containing added water, but does occur for solid K(6)[P(2)W(18)O(62)] in contact with water vapor.     

DNA-gold nanorod conjugates for remote control of localized gene expression by near infrared irradiation

Gold nanorods were attached to the gene of enhanced green fluorescence protein (EGFP) for the remote control of gene expression in living cells. The UV-vis spectroscopy, electrophoresis, and transmission electron microscopy (TEM) were used to study the optical and structural properties of the EGFP DNA and gold nanorod (EGFP-GNR) conjugates before and after femto-second near-infrared (NIR) laser irradiation. Upon NIR irradiation, the gold nanorods of EGFP-GNR conjugates underwent shape transformation that resulted in the release of EGFP DNA. When EGFP-GNR conjugates were delivered to cultured HeLa cells, induced GFP expression was specifically observed in cells that were locally exposed to NIR irradiation. Our results demonstrate the feasibility of using gold nanorods and NIR irradiation as means of remote control of gene expression in specific cells. This approach has potential applications in biological and medical studies.     

Functional silica nanoparticles synthesized by water-in-oil microemulsion processes

Water-in-oil (W/O) microemulsion is a well-suitable confined reacting medium for the synthesis of structured functional nanoparticles of controlled size and shape. During the last decade, it allowed the synthesis of multi-functional silica nanoparticles with morphologies as various as core–shell, homogenous dispersion or both together. The morphology and properties of the different intermediates and final materials obtained through this route are discussed in the light of UV–Vis–NIR spectroscopy, dynamic light scattering (DLS) and X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and magnetometer SQUID analysis.     

Photochromic hybrid materials of cucurbituril and polyoxometalates as photocatalysts under visible light

Two isostructural organic-inorganic hybrid solid materials based on cucurbituril derivatives and polyoxometalates, {[K(2)(H(2)O)(2)Na(2)(H(2)O)(2)Na(2)(H(2)O)(6)](P(2)W(18)O(62))(Me(10)Q(5))(2)}·~7H(2)O (1) and {[Rb(2)(H(2)O)(2)Na(2)(H(2)O)Na(2)(H(2)O)(4)](P(2)W(18)O(62))(Me(10)Q(5))(2)}·~8H(2)O (2), which exhibit reversible photochromic properties as well as excellent photocatalytic activities toward the degradation of methyl orange (MO) and rhodamine-B (RB) under visible light irradiation, are reported.     

Probing Distance‐Dependent Plasmon‐Enhanced Near‐Infrared Fluorescence Using Polyelectrolyte Multilayers as Dielectric Spacers

Owing to their applications in biodetection and molecular bioimaging, near‐infrared (NIR) fluorescent dyes are being extensively investigated. Most of the existing NIR dyes exhibit poor quantum yield, which hinders their translation to preclinical and clinical settings. Plasmonic nanostructures are known to act as tiny antennae for efficiently focusing the electromagnetic field into nanoscale volumes. The fluorescence emission from NIR dyes can be enhanced by more than thousand times by precisely placing them in proximity to gold nanorods. We have employed polyelectrolyte multilayers fabricated using layer‐by‐layer assembly as dielectric spacers for precisely tuning the distance between gold nanorods and NIR dyes. The aspect ratio of the gold nanorods was tuned to match the longitudinal localized surface plasmon resonance wavelength with the absorption maximum of the NIR dye to maximize the plasmonically enhanced fluorescence. The design criteria derived from this study lays the groundwork for ultrabright fluorescence bullets for in vitro and in vivo molecular bioimaging.     

A unique approach to development of near-infrared fluorescent sensors for in vivo imaging

Near-infrared (NIR) fluorescent sensors have emerged as promising molecular tools for imaging biomolecules in living systems. However, NIR fluorescent sensors are very challenging to be developed. Herein, we describe the discovery of a new class of NIR fluorescent dyes represented by 1a/1c/1e, which are superior to the traditional 7-hydroxycoumarin and fluorescein with both absorption and emission in the NIR region while retaining an optically tunable hydroxyl group. Quantum chemical calculations with the B3LYP exchange functional employing 6-31G(d) basis sets provide insights into the optical property distinctions between 1a/1c/1e and their alkoxy derivatives. The unique optical properties of the new type of fluorescent dyes can be exploited as a useful strategy for development of NIR fluorescent sensors. Employing this strategy, two different types of NIR fluorescent sensors, NIR-H(2)O(2) and NIR-thiol, for H(2)O(2) and thiols, respectively, were constructed. These novel sensors respond to H(2)O(2) or thiols with a large turn-on NIR fluorescence signal upon excitation in the NIR region. Furthermore, NIR-H(2)O(2) and NIR-thiol are capable of imaging endogenously produced H(2)O(2) and thiols, respectively, not only in living cells but also in living mice, demonstrating the value of the new NIR fluorescent sensor design strategy. The new type of NIR dyes presented herein may open up new opportunities for the development of NIR fluorescent sensors based on the hydroxyl functionalized reactive sites for biological imaging applications in living animals.     

Au nanorods decorated TiO2 nanobelts with enhanced full solar spectrum photocatalytic antibacterial activity and the sterilization file cabinet application

TiO₂ photocatalysts have been widely studied and applied for removing bacteria, but its antibacterial efficiency is limited to the ultraviolet (UV) range of the solar spectrum. In this work, we use the gold (Au) nanorods to enhance the visible and near-infrared (NIR) light absorption of TiO₂ NBs, a typical UV light photocatalyst, thus the enhancement of its full solar spectrum (UV, visible and NIR) photocatalytic antibacterial properties is achieved. Preliminary surface plasmon resonance (SPR) enhancement photocatalytic antibacterial mechanism is suggested. On one hand, transverse and longitudinal SPR of Au NRs is beneficial for visible and NIR light utilization. On the other hand, Au NRs combined with TiO₂ NBs to form the heterostructure, which can improve the photogenerated carrier separation and direct electron transfer increases the hot electron concentration while Au NRs as the electron channel can well restrain charge recombination, finally produces the high yield of radical oxygen species and exhibits a superior antibacterial efficiency. Furthermore, we design a sterilization file cabinet with Au NR/TiO₂ NB heterostructures as the photocatalytic coating plates. Our study reveals that Au NR/TiO₂ NB heterostructure is a potential candidate for sterilization of bacteria and archives protection.