Nanogap Plasmonic Structures Fabricated by Switchable Capillary‐Force Driven Self‐Assembly for Localized Sensing of Anticancer Medicines with Microfluidic SERS

Nanogap plasmonic structures, which can strongly enhance electromagnetic fields, enable widespread applications in surface‐enhanced Raman spectroscopy (SERS) sensing. Although the directed self‐assembly strategy has been adopted for the fabrication of micro/nanostructures on open surfaces, fabrication of nanogap plasmonic structures on complex substrates or at designated locations still remains a grand challenge. Here, a switchable self‐assembly method is developed to manufacture 3D nanogap plasmonic structures by combining supercritical drying and capillary‐force driven self‐assembly (CFSA) of micropillars fabricated by laser printing. The polymer pillars can stay upright during solvent development via supercritical drying, and then can form the nanogap after metal coating and subsequent CFSA. Due to the excellent flexibility of this method, diverse patterned plasmonic nanogap structures can be fabricated on planar or nonplanar substrates for SERS. The measured SERS signals of different patterned nanogaps in fluidic environment show a maximum enhancement factor ≈8 × 10⁷. Such nanostructures in microchannels also allow localized sensing for anticancer drugs (doxorubicin). Resulting from the marriage of top‐down and self‐assembly techniques, this method provides a facile, effective, and controllable approach for creating nanogap enabled SERS devices in fluidic channels, and hence can advance applications in precision medicine.     

In Situ Functionalization of Stable 3D Nest‐Like Networks in Confined Channels for Microfluidic Enrichment and Detection

Construction of stable 3D networks directly on the inner wall of microchannels is of great importance for various microfluidic applications. 3D nest‐like networks with large contact surface areas and excellent structural stability are fabricated via a facile, template‐free, continuous fluid construction process directly in confined microchannels. Bovine serum albumin (BSA) is chosen as a model albumin to test the adsorption of the network modified microchannel to the target albumin. The high structural stability of the networks is confirmed both by finite element analysis (FEA) simulation and recycling experiments for BSA enrichment. ZnS shells are fabricated based on the original 3D Zn(OH)F networks through in situ chemical conversion. The nest‐like networks decorated with Ag nanoparticles (NPs) serve as 3D substrates for surface‐enhanced Raman scattering (SERS), exhibiting excellent sensitivity for rapid detection of trace 10^?12 mol L^?1 (1 pM) BSA. Three different gap sizes between Ag NPs in the 3D geometry create a large number of SERS hot spots that contribute to the high sensitivity of the networks. Furthermore, a transparent, flexible, microfluidic device containing the 3D nest‐like structures exhibits excellent recyclability and flexible stability for trace BSA enrichment, showing potential for application in online SERS detection.     

Micro‐/Nanostructured Highly Crystalline Organic Semiconductor Films for Surface‐Enhanced Raman Spectroscopy Applications

The utilization of inorganic semiconductors for surface‐enhanced Raman spectroscopy (SERS) has attracted enormous interest. However, despite the technological relevance of organic semiconductors for enabling inexpensive, large‐area, and flexible devices via solution processing techniques, these π‐conjugated systems have never been investigated for SERS applications. Here for the first time, a simple and versatile approach is demonstrated for the fabrication of novel SERS platforms based on micro‐/nanostructured 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT) thin films via an oblique‐angle vapor deposition. The morphology of C8‐BTBT thin films is manipulated by varying the deposition angle, thus achieving highly favorable 3D vertically aligned ribbon‐like micro‐/nanostructures for a 90° deposition angle. By combining C8‐BTBT semiconductor films with a nanoscopic thin Au layer, remarkable SERS responses are achieved in terms of enhancement (≈10⁸), stability (>90 d), and reproducibility (RSD < 0.14), indicating the great promise of Au/C8‐BTBT films as SERS platforms. Our results demonstrate the first example of an organic semiconductor‐based SERS platform with excellent detection characteristics, indicating that π‐conjugated organic semiconductors have a great potential for SERS applications.     

Ultrasonication‐Induced Self‐Assembled Fixed Nanogap Arrays of Monomeric Plasmonic Nanoparticles inside Nanopores

Monomeric gold (Au) and silver (Ag) nanoparticle (NP) arrays are self‐assembled uniformly into anodized aluminium oxide (AAO) nanopores with a high homogeneity of greater than 95%, using ultrasonication. The monomeric metal NP array exhibits asymmetric plasmonic absorption due to Fano‐like resonance as interpreted by finite‐difference time‐domain (FDTD) simulation for the numbers up to 127 AuNPs. To examine gap distance‐dependent collective‐plasmonic resonance, the different dimensions of S, M, and L arrays of the AuNP diameters/the gap distances of ≈36 nm/≈66 nm, ≈45 nm/≈56 nm, and ≈77 nm/≈12 nm, respectively, are prepared. Metal NP arrays with an invariable nanogap of ≈50 nm can provide consistent surface‐enhanced Raman scattering (SERS) intensities for Rhodamine 6G (Rh6G) with a relative standard deviation (RSD) of 3.8–5.4%. Monomeric arrays can provide an effective platform for 2D hot‐electron excitation, as evidenced by the SERS peak‐changes of 4‐nitrobenzenethiol (4‐NBT) adsorbed on AgNP arrays with a power density of ≈0.25 mW µm^‐2 at 514 and 633 nm. For practical purposes, the bacteria captured by 4‐mercaptophenylboronic acid are found to be easily destroyed under visible laser excitation at 514 nm with a power density of ≈14 mW µm^‐2 for 60 min using Ag due to efficient plasmonic‐electron transfer.     

Direct‐Laser‐Writing of Metal Sulfide‐Graphene Nanocomposite Photoelectrode toward Sensitive Photoelectrochemical Sensing

Here, a facile approach for the in situ fabrication of metal sulfide (MS)‐graphene (G) nanocomposite, CdS‐G and PbS‐G, on indium?tin oxide (ITO) glass is demonstrated using a simple and scalable direct‐laser‐writing method in ambient air. Through the CO₂ laser irradiation of a metal‐complex‐containing polyethersulfone layer on ITO glass, both the crystallization of laser‐induced MS (LIMS) and the formation of laser‐induced graphene (LIG) are synchronously achieved in one step, giving rise to a laser‐induced MS‐G nanocomposite photoelectrode, denoted as LI‐MS‐G@ITO. In such a laser‐scribing process, polyethersulfone not only acts as the carbon source to grow LIG but also provides an in situ source of S^2? to produce LIMS with the aids of carbothermic reduction of sulfur element in polyethersulfone. The obtained LI‐MS‐G@ITO inherits the porous network architecture of polyethersulfone‐derived LIG, in which the LIMS nanocrystals uniformly decorate the multilayered graphene sheets with good dispersion, presenting a fast and stable photocurrent response with high reproducibility, which, as a proof‐of‐concept, further facilitates the use of a LI‐CdS‐G@ITO photoanode as an efficient transducer for photoelectrochemical detection of Cu²⁺ with high sensitivity and selectivity. This work can offer a universal and versatile protocol for the in situ and synchronous fabrication of novel MS‐G nanocomposites for sensitive photoelectrochemical analysis.     

三束飞秒激光辐照下铜膜内电子非平衡热输运

首先采用有限元法数值计算了铜膜内的电子温度和晶格温度分布变化,揭示了铜膜内电子非平衡热输运时间随飞秒激光光束参量的变化情况。仿真结果表明,铜膜内的电子非平衡热输运时间会随着泵浦光束数量及脉冲能量密度的增加而增加,并且使用三束飞秒泵浦激光作用时,电子非平衡热输运时间比单脉冲作用时的电子非平衡热输运时间增加了3倍。其次使用三束飞秒激光泵浦的泵浦-探测实验系统进行验证。实验结果表明:通过用具有一定延时的三束飞秒泵浦激光作用铜膜时,铜膜表面的瞬态反射率出现三次突变,使电子非平衡热输运时间得到极大延长,从而大幅度消除激光加工热障,并提高加工的质量、精度和效率。     

Mesostructured Arrays of Nanometer‐spaced Gold Nanoparticles for Ultrahigh Number Density of SERS Hot Spots

A novel one‐trough synthesis via an air‐water interface is demonstrated to provide hexagonally packed arrays of densely spaced metallic nanoparticles (NPs). In the synthesis, a mesostructured polyoxometalate (POM)‐silicatropic template (PSS) is first self‐assembled at the air‐water interface; upon UV irradiation, anion exchange cycles enable the free‐floating PSS film to continuously uptake gold precursors from the solution subphase for diffusion‐controlled and POM‐site‐directed photoreduction inside the silica channels. NPs ≈ 2 nm can hence be homogeneously formed inside the silica‐surfactant channels until saturation. As revealed via X‐ray diffraction, small‐angle X‐ray scattering (SAXS), grazing incidence SAXS, and transmission electron microscopy, the Au NPs directed by the PSS template are arrayed into a 2D hexagonal lattice with inter‐channel spacing of 3.2 nm and a mean along‐channel NP spacing of 2.8 nm. This corresponds to an ultra‐high number density (≈10¹⁹ NPs cm^?3) of narrowly spaced Au NPs in the Au‐NP@PSS composite, leading to 3D densely deployed hot‐spots along and across the mesostructured POM‐silica channels for surface‐enhanced Raman scattering (SERS). Consequently, the Au‐NP@PSS composite exhibits prominent SERS with 4‐mercaptobenzoic acid (4‐MBA) adsorbed onto Au NPs. The best 4‐MBA detection limit is 5 nm , with corresponding SERS enhancement factors above 10⁸.     

Arrays of Cone‐Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface‐Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls

A new, highly sensitive and uniform three‐dimensional (3D) hybrid surface‐enhanced Raman scattering (SERS) substrate has been achieved via simultaneously assembling small Ag nanoparticles (Ag‐NPs) and large Ag spheres onto the side surface and the top ends of large‐scale vertically aligned cone‐shaped ZnO nanorods (ZnO‐NRs), respectively. This 3D hybrid substrate manifests high SERS sensitivity to rhodamine and a detection limit as low as 10^?11 M to polychlorinated biphenyl (PCB) 77—a kind of persistent organic pollutants as global environmental hazard. Three kinds of inter‐Ag‐NP gaps in 3D geometry create a huge number of SERS “hot spots” that mainly contribute to the high SERS sensitivity. Moreover, the supporting chemical enhancement effect of ZnO‐NRs and the better enrichment effect ascribed to the large surface area of the substrate also help to achieve a lower detection limit. The arrays of cone‐shaped ZnO‐NRs decorated with Ag‐NPs on their side surface and large Ag spheres on the top ends have potentials in SERS‐based rapid detection of trace PCBs.     

Multiarray Nanopattern Electronic Nose (E‐Nose) by High‐Resolution Top‐Down Nanolithography

An electronic nose (E‐nose) is an artificial sensing device that mimics the human olfactory system using a multiarray sensor system. However, since the design and fabrication of multiarray sensing channels are significantly limited because of the requirement of time‐consuming and nonuniversal processes, the development of commercializable and high‐throughput fabrication approaches are critically required. Herein, high‐resolution top‐down lithography is developed for E‐nose fabrication for the first time. Five different metal oxide semiconductor (MOS) nanopattern channels (NiO, CuO, Cr₂O₃, SnO₂, and WO₃) are fabricated into multiarray sensors with high‐throughput using a unique lithographic approach that utilizes the sputtering of grains of the metals via low‐energy ion plasma bombardment. The nanopattern channels show i) high‐resolutions (15 nm scale), ii) high‐aspect‐ratios (11; 14 nm width and 150 nm height), and iii) ultrasmall grains (5.1 nm) with uniformity on a cm² scale, resulting in high sensitivity toward the target analytes. The E‐nose system, which is composed of five MOS nanopattern channels, can successfully distinguish seven different hazardous analytes, including volatile organic compounds and nitrogen‐containing compounds. It is expected that this unique lithography approach can provide a simple and reliable method for commercializable channel fabrication, and the E‐noses can have further applications in real‐life situations.     

High‐Density Hotspots Engineered by Naturally Piled‐Up Subwavelength Structures in Three‐Dimensional Copper Butterfly Wing Scales for Surface‐Enhanced Raman Scattering Detection

Very recently, wing scales of natural Lepidopterans (butterflies and moths) manifested themselves in providing excellent three dimensional (3D) hierarchical structures for surface‐enhanced Raman scattering (SERS) detection. But the origin of the observed enormous Raman enhancement of the analytes on 3D metallic replicas of butterfly wing scales has not been clarified yet, hindering a full utilization of this huge natural wealth with more than 175 000 3D morphologies. Herein, the 3D sub‐micrometer Cu structures replicated from butterfly wing scales are successfully tuned by modifying the Cu deposition time. An optimized Cu plating process (10 min in Cu deposition) yields replicas with the best conformal morphologies of original wing scales and in turn the best SERS performance. Simulation results show that the so‐called “rib‐structures” in Cu butterfly wing scales present naturally piled‐up hotspots where electromagnetic fields are substantially amplified, giving rise to a much higher hotspot density than in plain 2D Cu structures. Such a mechanism is further verified in several Cu replicas of scales from various butterfly species. This finding paves the way to the optimal scale candidates out of ca. 175 000 Lepidopteran species as bio‐templates to replicate for SERS applications, and thus helps bring affordable SERS substrates as consumables with high sensitivity, high reproducibility, and low cost to ordinary laboratories across the world.