A Novel Top‐Down Synthesis of Ultrathin 2D Boron Nanosheets for Multimodal Imaging‐Guided Cancer Therapy

Single atom nonmetal 2D nanomaterials have shown considerable potential in cancer nanomedicines, owing to their intriguing properties and biocompatibility. Herein, ultrathin boron nanosheets (B NSs) are prepared through a novel top‐down approach by coupling thermal oxidation etching and liquid exfoliation technologies, with controlled nanoscale thickness. Based on the PEGylated B NSs, a new photonic drug delivery platform is developed, which exhibits multiple promising features for cancer therapy and imaging, including: i) efficient NIR‐light‐to‐heat conversion with a high photothermal conversion efficiency of 42.5%, ii) high drug‐loading capacity and triggered drug release by NIR light and moderate acidic pH, iii) strong accumulation at tumor sites, iv) multimodal imaging properties (photoacoustic, photothermal, and fluorescence imaging), and v) complete tumor ablation and excellent biocompatibility. As far as it is known, this is the first report on the top‐down fabrication of ultrathin 2D B NSs by the combined thermal oxidation etching and liquid exfoliation, as well as their application as a multimodal imaging‐guided drug delivery platform. The newly prepared B NSs are also expected to provide a robust and useful 2D nanoplatform for various biomedical applications.     

Enhanced photoelectrochemical water-splitting effect with a bent ZnO nanorod photo anode decorated with Ag nanoparticles

Zinc oxide (ZnO) nanorods coated with silver (Ag) film on a polyethylene terephthalate (PET)flexible substrate were used as the photo anode for water splitting. The hybrid nanostructures were prepared via low-temperature hydrothermal growth and electron beam evaporation. The effects of plasmonic enhanced absorption, surface recombination inhibition and improved charge transport are investigated by varying the Ag thickness. Light trapping and absorption enhancement are further studied by optimizing the curvature of the PET substrates. The maximum short circuit current density (JSC, 0.616 mA cm -2) and the photoelectron conversion efficiency (PCE, 0.81%) are achieved with an optimized Ag film thickness of 10 nm and substrate bending radius of 6.0 mm. The maximum JSC and PCE are seven times and ten times, respectively, higher than those of the bare ZnO nanorods on flexible substrates without bending. The overall PEC performance improvement is attributed to the plasmonic effects induced by Ag film and improved charge transport due to inhibition of ZnO surface charge recombination. Enhanced light trapping (harvesting) induced by bending the PET substrates further improved the overall efficiency.     

Adhesion and growth of electrically active cortical neurons on polyethylenimine patterns microprinted onto PEO-PPO-PEO triblockcopolymer-coated hydrophobic surfaces

This paper describes the adhesion and growth of dissociated cortical neurons on chemically patterned surfaces over a time period of 30 days. The presence of neurons was demonstrated by measurement of spontaneous bioelectrical activity on a micropatterned multielectrode array. Chemical patterns were prepared with a combination of neurophobic layers of polyethylenoxide-polypropylenoxide-polyethylenoxide (PEO-PPO-PEO) triblockcopolymers adsorbed onto hydrophobic surfaces and neurophilic microprinted tracks of polyethylenimine (PEI). Results showed that commercially available PEO-PPO-PEO triblockcopolymers F108 and F127 (Synperonics, ICI) significantly reduced the adhesion of neuronal tissue when adsorbed on hydrophobic Polyimide (PI) and Fluorocarbon (FC) surfaces over a time period of eight days. In general, both F108- and F127-coated PI displayed equal or better neurophobic background properties after 30 days. Viability of neuronal tissue after 30 days on PEI microprinted F108- and F127-coated PI was comparable with relatively high viability factors between 0.9 and 1 (scale from 0 to 1). Summarizing, the strategy to combine the neurophobic adsorbed triblock-copolymers F108 and F127 onto hydrophobic surfaces with neurophilic microprinted PEI resulted in relatively long-term neuronal pattern preservation with high numbers of viable neurons present after 30 days.     

Junction‐Free Electrospun Ag Fiber Electrodes for Flexible Organic Light‐Emitting Diodes

Fabrication of junction‐free Ag fiber electrodes for flexible organic light‐emitting diodes (OLEDs) is demonstrated. The junction‐free Ag fiber electrodes are fabricated by electrospun polymer fibers used as an etch mask and wet etching of Ag thin film. This process facilitates surface roughness control, which is important in transparent electrodes based on metal wires to prevent electrical instability of the OLEDs. The transmittance and resistance of Ag fiber electrodes can be independently adjusted by controlling spinning time and Ag deposition thickness. The Ag fiber electrode shows a transmittance of 91.8% (at 550 nm) at a sheet resistance of 22.3 Ω □^?1, leading to the highest OLED efficiency. In addition, Ag fiber electrodes exhibit excellent mechanical durability, as shown by measuring the change in resistance under repeatable mechanical bending and various bending radii. The OLEDs with Ag fiber electrodes on a flexible substrate are successfully fabricated, and the OLEDs show an enhancement of EQE (≈19%) compared to commercial indium tin oxide electrodes.     

Preparation and characterization of luminescent nanocomposite film containing polyoxometalate

A nanosized composite film based on polyoxometalate anion [Eu(SiW₁₀VO₃₉)₂]¹⁵⁻ (EuSiWV) and polyethyleneimine (PEI) has been synthesized by layer-by-layer (LBL) self-assembly. The components and growth processes of the film have been determined by X-ray photoelectron spectra and ultraviolet-visible absorption spectra. The results showed that the composite film was formed by the alternate adsorption of EuSiWV and PEI, and the deposition process was quantitative and highly reproducible from layer to layer. Atomic force microscopy images indicated that the surface of the film was relatively uniform and smooth. The EuSiWV salt aggregated into nanoclusters with approximately 10 nm mean grain size, distributing on the surface uniformly. The surface roughness was approximately 2.4 nm. Fluorescence properties of the film were consistent with those of the solid sample, exhibiting obvious activity of fluorescence and incarnating the characteristic luminescence of Eu³⁺. In addition, the electrochemical behavior of the film has also been investigated, demonstrating that the electrochemical property of EuSiW₁₀V was fully maintained in the LBL film.     

High roughness Ag back reflector on a metal underlayer for thin film solar cell applications

The roughness development of Ag film was investigated for potential as a back reflector material in thin film solar cells on flexible stainless steel (STS) substrates. The influence of metal underlayers was evaluated in order to obtain a rough Ag film at a low deposition temperature (≤400 °C). By depositing Ag on a 100 nm Al underlayer to induce Ag–Al alloying, the film roughness was increased three times more than that of Ag films on bare STS at 400 °C. The Ag film deposited on an Al underlayer at 350 °C exhibited 75 nm roughness and uniformly distributed crystallites, which was effective for visible light scattering. The Ag–Al alloy phase was also controlled using the thickness ratio of Ag and Al. The present work clearly demonstrated that an Ag back reflector film with a higher roughness could be fabricated through inserting a metal underlayer at a deposition temperature much lower than the 500 °C that has been reported in earlier works.     

Antibacterial Efficacy of Sacrifical Anode Thin Films Combining Silver with Platinum Group Elements within a Bacteria‐Containing Human Plasma Clot

Silver (Ag) dots arrays (64 and 400 dots per mm²) are fabricated on a continuous platinum (Pt), palladium (Pd), or iridium (Ir) thin film (sacrifical anode systems for Ag) and for comparison on titanium (Ti) film (non‐sacrifical anode system for Ag) by sputter deposition and photolithographic patterning. The samples are embedded within a tissue‐like plasma clot matrix containing Staphylococcus aureus (S. aureus), cultivated for 24 h. Bacterial growth is analyzed by fluorescence microscopy. Among platinum group sacrifical anode elements and a dense Ag sample, only the high Ag ion releasing Ag–Ir system is able to inhibit the bacterial growth within the adjacent plasma clot matrix. This study demonstrates that the antibacterial efficiency of Ag coatings is reduced under tissue‐like conditions. However, the new sacrificial anode based Ag–Ir system can overcome this limitation.

     

Tuned optical properties of in-situ synthesized m-nitroaniline doped Ag/PVA nano-composites

Meta-nitroaniline (m-NA) doped silver/poly(vinylalcohol) (Ag/PVA) nanocomposites are prepared via in-situ reduction of silver salt by employing hydrazine hydrate (HH) in order to study the effect of the NLO active m-NA on the optical properties of nanoparticles of silver in the colloidal as well as self supported film form. Reduction of silver salt in aqueous alcoholic PVA with HH is done first followed by doping of the reaction mixture with m-NA. The UV-Visible absorption spectra show peak at about 400 nm for Ag nanoparticles due to surface plasmon resonance phenomenon, which gets blue shifted with the change in m-NA concentration. The Second Harmonic Generation (SHG) studies show improvement in intensity with increasing m-NA concentration up to a saturation point (approximately 2.52 wt% with respect to PVA). Further increase in m-NA concentration leads to decrease in SHG intensity. The solutions and the films are characterized by photoluminescence (PL), FTIR spectroscopy, XRD, SEM, TEM, and thermal analysis. m-NA doped composites showed better PL efficiency. SEM of the nanocomposite film shows uniform distribution of particles within the film. The particle size as shown by TEM is found to be less than 10 nm.     

氧化石墨烯/聚酰亚胺复合薄膜的制备及阻水性能

以石墨粉为原料,采用改进的Hummers法制备氧化石墨烯（GO）,采用原位聚合法制备GO/聚酰亚胺酸（PAA）前驱体,GO/PAA前驱体经高温固化处理后得到GO/聚酰亚胺（PI）复合薄膜;采用XRD、Raman、FTIR、AFM等表征手段对GO的结构进行表征;此外,研究了不同固化温度下PI薄膜的结构;最后测试了GO/PI复合薄膜的透湿率和力学性能。结果表明:GO为单层结构,厚度为1.26 nm。GO/PI复合薄膜表现出良好的阻水性能,当GO/PI复合薄膜中GO的添加量为0.025wt%、薄膜厚度为50 μm时,GO/PI复合薄膜的透湿率低至56.7 g（m2·d）-1。此外,0.025wt% GO/PI复合薄膜拉伸强度和断裂伸长率分别为150.8 MPa和13.5%,与PI薄膜（分别为126.9 MPa和8.1%）相比,分别增加了18.8%和66.7%。      

Si基片上Ag膜的微结构及光学常数研究

用真空蒸镀法在室温Si基片上制备了Ag薄膜 ,并用X射线衍射及反射式椭偏光谱技术对薄膜的微结构和光学常数进行了测试分析。结构分析表明 :制备的Ag膜晶体仍为面心立方结构 ,呈多晶状态 ,晶粒择优取向于 [111],平均晶粒尺寸约为 2 2 7nm ,晶格常数 ( 0 4 0 860nm)比标准值 ( 0 4 0 862nm)略小。在 2 5 0～ 83 0nm波长范围椭偏光谱测量结果表明 :Ag膜的折射率和消光系数分别在 0 15～ 1 4 9和 0 3 1～ 5 77之间。与块材相比 ,在块材的折射率大于一定值 ( 1 0 0～ 1 3 3 )时 ,Ag膜的折射率比块材的小 ,其余范围则增大 ;Ag膜的消光系数减小。并给出了一套较为可靠的、具有实用价值的Ag薄膜光学常数。     

Large enhancement of fluorescence efficiency from CdSe/ZnS quantum dots induced by resonant coupling to spatially controlled surface plasmons

Nanoengineered fluorescent response is reported from semiconductor core-shell (CdSe/ZnS) quantum dots in proximity to the surface plasmon polariton field of periodic Ag nanoparticle arrays. Tuning the surface plasmon polariton resonance to the quantum dot exciton emission band results in an enhancement of up to approximately 50-fold in the overall fluorescence efficiency, in a design where each Ag nanoparticle is interconnected by a continuous Ag thin film. Propagating modes of surface plasmon resonances have a direct impact on the fluorescence enhancement.     

Adhesion characteristics of silver tracks screen-printed on polyimide with an environmental reliability test

Printable and flexible electronics are increasingly being used in numerous applications that are miniaturized, multi-functional and lightweight. Simultaneously, reliability issues of the printed and flexible electronic devices are getting more attention. The adhesion of screen-printed silver (Ag) tracks on a polyimide (PI) film was investigated after two kinds of the environmental reliability test: a constant-temperature storage test, and a steady-state temperature and humidity storage test. Atmospheric-pressure plasma (APP) was adopted on the PI film surface to improve the poor adhesion derived from the inherent hydrophobicity. The Ag tracks constructed via screen printing were sintered at 250 degrees C for 30 min in air using a box-type muffle furnace. Some samples were exposed under 85 degrees C and 85% relative humidity (RH) for various durations (24, 72, 168 and 500 h), and others were aged at 85 degrees C with same durations to compare the influence of moisture on the adhesion. The adhesion of the screen-printed Ag tracks was evaluated by a roll-type 90 degrees peel test. The peel strength of the screen-printed Ag tracks decreased by 76.74% and 69.88% after 500 h run of the 85 degrees C/85% RH test, and the aging test, respectively. The weakest adhesion was 4.98 gf/mm after the 500 h run of the 85 degrees C/85% RH test. To demonstrate these experimental results, the microstructural evolution and chemical bonding states of the interfacial surfaces were characterized using a field emission scanning electron microscope (FE-SEM), and X-ray photoelectron spectroscope (XPS), respectively.     

Novel Mn3[Co(CN)6]2@SiO2@Ag Core–Shell Nanocube: Enhanced Two‐Photon Fluorescence and Magnetic Resonance Dual‐Modal Imaging‐Guided Photothermal and Chemo‐therapy

The versatile Mn₃[Co(CN)₆]₂@SiO₂@Ag core–shell NCs are prepared by a simple coprecipitation method. Ag nanoparticles with an average diameter of 12 nm deposited on the surface of Mn₃[Co(CN)₆]₂@SiO₂ through S–Ag bonding are fabricated in ethanol solution by reducing silver nitrate (AgNO₃) with NaBH₄. The NCs possess T₁–T₂ dual‐modal magnetic resonance imaging ability. The inner Prussian blue analogs (PBAs) Mn₃[Co(CN)₆]₂ exhibit bright two‐photon fluorescence (TPF) imaging when excited at 730 nm. Moreover, the TPF imaging intensity displays 1.85‐fold enhancement after loading of Ag nanoparticles. Besides, the sample also has multicolor fluorescence imaging ability under 403, 488, and 543 nm single photon excitation. The as‐synthesized Mn₃[Co(CN)₆]₂@SiO₂@Ag NCs show a DOX loading capacity of 600 mg g⁻¹ and exhibit an excellent ability of near‐infrared (NIR)‐responsive drug release and photothermal therapy (PTT) which is induced from the relative high absorbance in NIR region. The combined chemotherapy and PTT against cancer cells in vitro test shows high therapeutic efficiency. The multimodal treatment and imaging could lead to this material a potential multifunctional system for biomedical diagnosis and therapy.     

纳米ZnS/PVDF复合膜的制备及其光学性能

以醋酸锌(ZnAC₂ ·2H₂O)和聚偏氟乙烯(PVDF)为原料, N-N-二甲基甲酰胺为溶剂, 采用溶胶-凝胶原位复合的方法制备纳米硫化锌/聚偏氟乙烯复合膜。X射线衍射和透射电镜分析表明, 复合膜中的ZnS晶粒分布均匀, 平均尺寸在3~7nm之间, 具有明显的立方相结构。紫外-可见吸收光谱和荧光光谱分析表明, 随着ZnS晶粒度的减小, 复合膜的吸收边出现从310→270nm的蓝移, 该复合膜中同时存在368nm的激子复合发光和429nm自激活发光。分散剂的加入不会对复合膜的荧光性能产生本质的影响, 但可以使ZnS生长速度减慢, 分散更均匀。      

Light‐Responsive Biodegradable Nanorattles for Cancer Theranostics

Cancer nanotheranostics, integrating both diagnostic and therapeutic functions into nanoscale agents, are advanced solutions for cancer management. Herein, a light‐responsive biodegradable nanorattle‐based perfluoropentane‐(PFP)‐filled mesoporous‐silica‐film‐coated gold nanorod (GNR@SiO₂‐PFP) is strategically designed and prepared for enhanced ultrasound (US)/photoacoustic (PA) dual‐modality imaging guided photothermal therapy of melanoma. The as‐prepared nanorattles are composed of a thin mesoporous silica film as the shell, which endows the nanoplatform with flexible morphology and excellent biodegradability, as well as large cavity for PFP filling. Upon 808 nm laser irradiation, the loaded PFP will undergo a liquid–gas phase transition due to the heat generation from GNRs, thus generating nanobubbles followed by the coalescence into microbubbles. The conversion of nanobubbles to microbubbles can improve the intratumoral permeation and retention in nonmicrovascular tissue, as well as enhance the tumor‐targeted US imaging signals. This nanotheranostic platform exhibits excellent biocompatibility and biodegradability, distinct gas bubbling phenomenon, good US/PA imaging contrast, and remarkable photothermal efficiency. The results demonstrate that the GNR@SiO₂‐PFP nanorattles hold great potential for cancer nanotheranostics.     

原位氨基化氧化石墨烯/聚酰亚胺复合材料的制备及性能

以1,4-双（4-氨基-2-三氟甲基苯氧基）苯（6FAPB）和3,3',4,4'-二苯醚四酸二酐（ODPA）为合成聚酰亚胺（PI）的单体,首先采用原位氨基化方法使氧化石墨烯（GO）与6FAPB反应转变为原位氨基化GO,再与ODPA和剩余的6FAPB发生聚合反应得到原位氨基化GO/聚酰胺酸（PAA）溶液。涂膜后,经热酰亚胺化制备出GO质量分数分别为0.05wt%、0.1wt%、0.3wt%、0.5wt%和1.0wt%的原位氨基化GO/PI复合材料膜。利用FTIR、XPS、XRD、UV-vis、TGA、TMA、SEM、拉伸性能测试及接触角测试对原位氨基化GO/PI复合材料的结构和性能进行表征。结果表明,原位氨基化使GO以化学键与PI大分子链连接,有利于GO在复合材料基体中的稳定和均匀分散。XRD结果表明,所得到的原位氨基化GO/PI复合材料膜均为无定型结构。随GO质量分数增加,原位氨基化GO/PI复合材料薄膜的光学透明性急剧降低,但力学性能和热稳定性有一定提高。当GO的质量分数为1.0wt%时,原位氨基化GO/PI复合材料的拉伸强度由64 MPa增加到83 MPa,杨氏模量由1.67 GPa提高到2.10 GPa,10%热失重温度由593℃增加到597℃,玻璃化转变温度变化不大。由于热酰亚胺化后GO表面的大部分含氧官能团消失,原位氨基化GO/PI复合材料膜的吸水率由0.86%降低至0.58%,水接触角由72.5°增加到77.8°。     

AuCl4 ions-assisted fabrication of bimetallic {Poly(ethylenimine)-Ag/Au} multilayer polyelectrolyte film and application in electrocatalysis

Bimetallic {Poly(ethylenimine) (PEI)-Ag/Au} multilayer film was in situ simultaneously fabricated by alternating immersions of a substrate in PEI-Ag⁺ and AuCl₄⁻ solutions followed by chemical reduction with NaBH₄ solution. In the process, the AuCl₄⁻ ions not only play an important role of a reaction reagent, but also served as an assembly reagent. Au, Ag nanoparticles (NPs) were observed with a spherical morphology and well-dispersed in the composite multilayer film, and the size of Au NPs in the bimetallic {PEI-Ag/Au} multilayer film was smaller than that of the single Au NPs formed in {PEI/Au} multilayer films. It was also very interesting to observe that this bimetallic {PEI-Ag/Au} multilayer film exhibited more efficient electrocatalytic activity for the oxidation of ascorbic acid than the multilayer film containing only single Au or Ag NPs. These results indicated that this bimetallic composite multilayer film may be potentially applied in electrochemical biosensors.     

High resolution imaging analysis of CdSe/ZnS core–shell quantum dots (QDs) using Cs-corrected HR-TEM/STEM

CdSe/ZnS core–shell structured nano-crystal quantum dots (QDs) are ideal candidates for light-emission applications due to their high quantum efficiency, narrow-band, and particle-size-tunable photoluminescence. In particular, their small size results in the quantum confinement of semiconductor nano-crystals, which widens their energy gaps. In general, high resolution imaging analyses of QDs using a transmission electron microscope are very difficult due to their significantly small size. Successful imaging depends on the capabilities of TEM equipment and the contrast of the QDs sample relative to the supporting film. In this work, all imaging analyses were performed on a TEM equipped with a probe Cs corrector. The samples for observing QDs were prepared by drying each QDs solution on a lacey carbon Cu (300 mesh) grid previously coated with an ultra-thin graphene monolayer (thickness = 0.3 nm), due to the need to minimize the effect of the supported film.     

Normal and surface-enhanced Raman spectroscopy of nitroazobenzene submonolayers and multilayers on carbon and silver surfaces

Raman and ultraviolet-visible (UV-Vis) absorption spectra were obtained for nitroazobenzene (NAB) chemisorbed on smooth and rough silver, and they were compared to published spectra for NAB on sp(2) hybridized pyrolyzed photoresist film (PPF) surfaces. High signal-to-noise ratio Raman spectra were obtained for 4.5 nm thick NAB films on PPF and smooth Ag due to significant enhancement of the NAB scattering relative to that observed in solution. The UV-Vis spectra of chemisorbed NAB exhibited a significant shift toward longer wavelength, thus bringing the NAB absorption closer to the 514.5 nm laser wavelength. The red shift was larger for PPF than for smooth Ag, consistent with the approximately 5x stronger Raman signal obtained on PPF. Deposition of Ag onto quartz without a chromium adhesion layer produced a rough Ag surface that enhanced the Raman spectrum of chemisorbed NAB by a factor of approximately 1000, as expected for roughened Ag due to electromagnetic field enhancement. The strong Raman signal permitted observation of NAB at low coverage and revealed changes in the NAB spectrum as the film progressed from submonolayer to multilayer thicknesses. Finally, deposition of Ag onto PPF/NAB samples through a metal grid produced Ag squares on top of the NAB, which enhanced the Raman scattering of the NAB layer by a factor of approximately 100. Deposition of a final conducting film on the Ag squares should permit in situ observation of a wide range of molecules in operating molecular electronic junctions.     

Ultrafast deposition of silicon nitride and semiconductor silicon thin films by hot wire chemical vapor deposition

The technology of Hot Wire Chemical Vapor Deposition (HWCVD) or Catalytic Chemical Vapor Deposition (Cat-CVD) has made great progress during the last couple of years. This review discusses examples of significant progress. Specifically, silicon nitride deposition by HWCVD (HW-SiN_x) is highlighted, as well as thin film silicon single junction and multijunction junction solar cells. The application of HW-SiN_x at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency and preliminary tests of our transparent and dense material obtained at record high deposition rates of 7.3 nm/s yielded 14.9% efficiency. We also present recent progress on Hot-Wire deposited thin film solar cells. The cell efficiency reached for (nanocrystalline) nc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.6%. Such cells, used in triple junction cells together with Hot-Wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.9% efficiency. Further, in our research on utilizing the HWCVD technology for roll-to-roll production of flexible thin film solar cells we recently achieved experimental laboratory scale tandem modules with HWCVD active layers with initial efficiencies of 7.4% at an aperture area of 25 cm².