AbstractElectrochemically up-regulated surface-enhanced Raman spectroscopy (E-SERS) effectively increases Raman signal intensities. However, the instrumental requirements and the conventional measurement conditions in an electrolyte cell have hampered its application in fast and on-site detection. To circumvent the inconveniences of E-SERS, we propose a self-energizing substrate that provides electrical potential by converting film deformation from a finger press into stored electrical energy. The substrate combines an energy conversion film and a SERS-active Ag nanowire layer. A composite film prepared from a piezoelectric polymer matrix and surface-engineered rGO that simultaneously presents high permittivity and low dielectric loss is the key component herein. Using our substrate, increased E-SERS signals up to 10 times from a variety of molecules were obtained in the open air. Various tests on real-life sample surfaces demonstrated the potentials of the substrate in fast on-site detection.

Raman-Signalverstärkung per Fingerdruck wurde durch Kombination eines flexiblen, piezoelektrischen und dielektrischen Energieumwandel- und Speicherfilms mit Silbernanodrahtschichten erhalten. In der Zuschrift auf S. 2693 ff. beschreiben Y. Zhang, Q. An et al. ein selbstanregendes SERS-Trägermaterial (SERS=oberflächenverstärkte Raman-Streuung), das Filmdeformationen in gespeicherte elektrische Energie umwandeln kann, die dann Elektronen in eine Silbernanodrahtschicht injiziert und die darin gemessenen SERS-Signale erhöht.

Effective and robust interfacial protein retention lies at the heart of the fabrication of protein-based functional interfaces, which is potentially applicable in catalysis, medical therapy, antifouling, and smart devices, but remains challenging due to the sensitive nature of proteins. This study reports a general protein retention strategy to spatial-temporally confine various types of proteins at interfacial regions. The proteins were preserved in mesoporous silica nanoparticles embedded in covalently woven multilayers. It is worth noting that the protein retention strategy effectively preserves the catalytic capabilities of the proteins, and the multilayer structure is robust enough to withstand the bubbling catalytic reactions and could be repeatedly used due to conservation of proteins. The spatiotemporal retention of proteins could be adjusted by varying the number of capping layers. Furthermore, we demonstrate that the protein-loaded interfacial layers could not only be used to construct catalytic-active interfaces, but also be integrated as the power-generating unit to propel a macroscopic floating device.

Multifunctional plasmonic particles serving simultaneously as catalysts and label-free reporting agents are highly pursued due to their great potential in enhancing reaction operational efficiencies. Copper is an abundant and economic resource, and it possesses practical applicability in industries, but no dual-functional copper-based catalytic and self-reporting particles have been reported so far. This study proposes a facile strategy to prepare high-performance dual-functional copper-based composite particles that catalyze reactions and simultaneously serve as a SERS (surface enhanced Raman spectra) active, label-free reporting agent. Polyelectrolyte-modified reduced graphene oxide particles are used as the reactive precursors in the fabrication method. Upon adding Cu(NO3)2 solutions into the precursor dispersions, composite particles comprised by copper/copper oxide core and polyelectrolyte–graphene shell were facilely obtained under sonication. The as-prepared composite particles efficiently catalyzed the conversion of 4-nitrophenol to 4-aminophenol and simultaneously acted as the SERS-active substrate to give enhanced Raman spectra of the produced 4-aminophenol. Taking advantage of the assembling capabilities of polyelectrolyte shells, the composite particles could be further assembled onto a planar substrate to catalyze organic reactions, facilitating their application in various conditions. We expect this report to promote the fabrication and application of copper-based multifunctional particles.

A variety of small molecules with diameters around 1 nm possess a range of functions, such as antibiotic, antimicrobic, anticoagulant, pesticidal and chemotherapy effects, making these molecules especially useful in various applications ranging from medical treatment to environmental microbiological control. However, the long-term steady delivery (release or permeation) of these small molecules with adjustable and controllable speeds has remained an especially challenging task. In this study, we prepared covalently cross-linked free-standing few-layered GO films using a layer-by-layer technique in combination with photochemical cross-linkages, and achieved a controlled release of positively charged, negatively charged, and zwitterionic small molecules with adjustable and controllable speeds. The steady delivery of the small molecule lasted up to 9 days. Other functionalities, such as graphene-enhanced Raman spectra and electrochemical properties that could also be integrated or employed in delivery systems, were also studied for our films. We expect the special molecular delivery properties of our films to lead to new possibilities in drug/fertilizer delivery and environmental microbiological control applications.

Interfacial properties including permeation, catalytic efficiency, Raman signal enhancement capabilities, and cell spreading efficiencies are important features that determine material functionality and applications. Here, we propose a facile method to adjust the above-mentioned properties by controlling the cross-linking degrees of multilayer using a photoactive molecule. After treating the cross-linked films in basic solutions, films with different cross-linking degrees presented varying residue thicknesses and film morphologies. As a result, these different films possessed distinct molecular loading and release characteristics. In addition, gold nanoparticles (AuNPs) of different morphological traits were generated by redox reactions coupled with diffusion within these films. The AuNP–polyelectrolyte obtained from the polyelectrolyte films of the medium cross-linking degrees displayed the highest catalytic efficiency and signal enhancement capabilities. Furthermore, cells responded to the variation of film cross-linking degrees, and on the films with the highest cross-linking degree, cells adhered with the highest speed. We expect this report to provide a general interfacial material engineering strategy for material designs.Keywords: catalytic efficiency; cell spreading; interfacial permeation; layer-by-layer; photochemical cross-linking; signal enhancement capability;

The layer-by-layer (LbL) technique has been intensively investigated as a straightforward method for the incorporation of drug molecules or other bioactive species, enabling retarded release in drug delivery devices, in bioactive interfaces, in tissue engineering, and in regenerative medicine. The preparation of crosslinked LbL multilayers with embedded drug reservoirs for delayed release remains a challenging task, however. In the present study we have developed a method for the simultaneous utilisation of covalent interlayer linkages and drug reservoirs that can hold model drug molecules. A strategy of post-infiltration of photoactive bifunctional small molecules followed by UV irradiation has been employed for crosslinking the LbL multilayers, incorporating poly(amido amine) (PAMAM) molecules, which serve as a drug reservoir. The covalent linkage significantly alters the release profile of the model drug from the multilayers, with retarded release of hydrophobic molecules from a solvent, and enabling the loaded multilayers to withstand rinsing with 75% ethanol, the most commonly used sterilization procedure.

A high-performance visible-light-active photocatalyst is prepared using the polyelectrolyte/exfoliated titania nanosheet/graphene oxide (GO) precursor by flocculation followed by calcination. The polyelectrolyte poly(diallyl-dimethyl-ammonium chloride) serves not only as an effective binder to precipitate GO and titania nanosheets, but also boosts the overall performance of the catalyst significantly. Unlike most titania nanosheet-based catalysts reported in the literature, the composite absorbs light in the UV-Vis-NIR range. Its decomposition rate of methylene blue is 98% under visible light. This novel strategy of using a polymer to enhance the catalytic performance of titania nanosheet-based catalysts affords immense potential in designing and fabricating next-generation photocatalysts with high efficiency.

To fabricate functionally integrated hybrid nanoparticles holds high importance in biomedical applications and is still a challenging task. In this study, we report the first reduced graphene oxide (rGO)-nobel metal hybrid particles that present simultaneously the photothermal and surface-enhanced Raman spectroscopy (SERS) effect from the inorganic part and drug loading, dispersibility, and controllability features from LbL polyelectrolyte multilayers. The hybrid particles where spiky noble metal particles were wrapped within rGO-polyelectrolyte layers were prepared by a facile and controllable method. rGO template modified using polyethylenimine (PEI) and poly(acrylic acid) (PAA) via layer-by-layer technology served as the reactive precursors, and the morphologies of the particles could be facilely controlled via controlling the number of bilayers around the rGO template. The hybrid particle presented low cytotoxicity. After loading doxorubicin hydrochloride, the particles effectively induced cell death, and photothermal treatment further decreased cell viability. rGO-Ag hybrid particles could be prepared similarly. We expect the reported method provides an effective strategy to prepare rGO-noble metal hybrid nanoparticles that find potential biomedical applications.Keywords: gold nanoparticles; graphene; hybrid nanoparticles; layer-by-layer; photothermal; surface-enhanced Raman scattering

A “nano-net” superstratum strategy is developed to stabilize layer-by-layer (LbL) films that incorporate nanoparticles. The superstratum immobilizes silica, gold, or magnetic nanoparticles and at the same time is permeable to small molecules. Unlike most strategies to stabilize LbL multilayers reported in the literature, our strategy does not directly cross-link the nanoparticles and polymers in the adjacent layer, thus circumventing the tedious processes of (surface) modification of the nanoparticles or polymers. The unique advantage of our strategy is further employed in the preparation of a model functional device, where mesoporous silica nanoparticles are held in the composite multilayers with enhanced stabilities. A model drug, methylene blue, is then loaded in large amounts due to the porous structure of the silica particles, and could be released in a delayed manner up to 55 h.

Photothermal materials prepared from graphene and Au nanoparticles have received increasing attentions in various fields ranging from smart devices to advanced medical therapies. In this report, we studied the photothermal transition effects of LbL AuNS/rGO (AuNS: Au nanosheets) films under laser irradiation at 940 nm and comparisons were made with the film of rGO or AuNSs, wherein a single type of photothermal effective species exists. The results indicate that the hybrid LbL AuNS/rGO films displayed enhanced photothermal effects compared with the rGO or AuNSs films. The photothermal performance of the hybrid AuNS/rGO films deteriorated over repeated use or long-term laser irradiation, but the ultimate performance after irradiation was still better than that of the rGO or AuNS films. The hybrid film was able to load the model drug methylene blue (MB), and release MB 4 times faster with NIR irradiation than without, suggesting potential application in the combined chemical and thermal therapies. Thus, the hybrid film of AuNS/rGO is recommended when short-term or few-cycle photothermal applications are required. In comparison, rGO multilayered film better suits long-term or repeated photothermal applications, wherein stable photothermal performance is required.

Constructing stable and reliable interfaces around pseudo two-dimensional clay materials is a key process in achieving advanced and reliable performance of related composite materials. However, the effective surface modification of pseudo two-dimensional clay has been a challenging research topic. In this study, we have developed an effective and facile method for the interfacial modification of magnetic montmorillonite (MMT) nanocomposite by using covalent layer-by-layer (LbL) assembly. The method involves conventional LbL assembly around the magnetic MMT followed by infiltration of a bifunctional photoactive small molecule and then covalent cross-linking of the LbL multilayers upon UV irradiation. After covalent LbL modification, the nanocomposite presented ample organic species around its interfaces and displayed stable organic interfaces even in extreme solution conditions such as in basic (pH =14) solutions. The covalent cross-linking of the multilayers proved to be indispensable in keeping the LbL multilayers stable around the MMT composites. After modification, the composite particles kept their magnetic properties. In addition, the release profile of the composite particles for methyl blue indicated that the composite particles preserved the capacity to carry loads and release them in retarded speed. This method will potentially integrate the merits of LbL multilayers with MMT to achieve advanced functional materials.

In this paper, we have developed a facile and general strategy to enhance the stability of multilayers incorporating nanoparticles and the weak polyelectrolyte poly(allylamine hydrochloride) (PAH). Using Fe3O4 nanoparticles (Fe3O4 NPs) and Au nanoparticles (Au NPs) as separate model systems, after multilayers of nanoparticles and PAH were constructed employing the layer-by-layer (LbL) technique, 4,4′-diazostilbene-2,2′-disulphonic acid disodium salt (DAS) was post-infiltrated into the multilayers and subsequent photochemical cross-linking was completed under UV irradiation. The stability of multilayers with Fe3O4 NPs and Au NPs were both improved significantly, and less than 15% of the nanoparticles were lost from the multilayers after an intensive agitation. The UV-visible spectroscopy and atomic force microscopy measurements supported the improvement of the stability of the multilayers.

We develop a facile method to immobilize cucurbituril on silicon substrates through photochemical reaction with azido groups. Combining photolithography and the competitive molecular recognition between CB[7] and acridine orange base or 1-adamantanecarboxylic acid, a patterned surface with reversible fluorescence emission can be obtained.

In this paper, we have demonstrated a facile strategy to prepare molecularly imprinted layer-by-layer nanostructured films. This strategy has circumvented the requirement of using photocross-linkable polymers, which suffered from tedious synthetic processes in the construction of surface molecular imprinting in layer-by-layer (SMI-LbL) devices. The described SMI-LbL device was constructed by employing the traditional construction procedures of LbL systems, followed by the postinfiltration of bifunctional photosensitive cross-linking agent 4,4′-diazostilbene-2,2′-disulfonic acid disodium salt into the prepared multilayers, and subsequent photocross-linking. A robust SMI-LbL device with high fatigue-resistance was achieved. The preparation conditions have been optimized to achieve repeated unloading and rebinding of the targeting molecule with high fidelity. The combination of templating and cross-linking is the core factor to achieve high fidelity and high efficiency of the SMI-LbL device.Keywords: diazostilbene; layer-by-layer; photo-cross-linking; self-assembly; supramolecular; surface molecular imprinting;

The layer-by-layer (LbL) technique has been intensively investigated as a straightforward method for the incorporation of drug molecules or other bioactive species, enabling retarded release in drug delivery devices, in bioactive interfaces, in tissue engineering, and in regenerative medicine. The preparation of crosslinked LbL multilayers with embedded drug reservoirs for delayed release remains a challenging task, however. In the present study we have developed a method for the simultaneous utilisation of covalent interlayer linkages and drug reservoirs that can hold model drug molecules. A strategy of post-infiltration of photoactive bifunctional small molecules followed by UV irradiation has been employed for crosslinking the LbL multilayers, incorporating poly(amido amine) (PAMAM) molecules, which serve as a drug reservoir. The covalent linkage significantly alters the release profile of the model drug from the multilayers, with retarded release of hydrophobic molecules from a solvent, and enabling the loaded multilayers to withstand rinsing with 75% ethanol, the most commonly used sterilization procedure.

In this paper, we have developed a facile and general strategy to enhance the stability of multilayers incorporating nanoparticles and the weak polyelectrolyte poly(allylamine hydrochloride) (PAH). Using Fe3O4 nanoparticles (Fe3O4 NPs) and Au nanoparticles (Au NPs) as separate model systems, after multilayers of nanoparticles and PAH were constructed employing the layer-by-layer (LbL) technique, 4,4′-diazostilbene-2,2′-disulphonic acid disodium salt (DAS) was post-infiltrated into the multilayers and subsequent photochemical cross-linking was completed under UV irradiation. The stability of multilayers with Fe3O4 NPs and Au NPs were both improved significantly, and less than 15% of the nanoparticles were lost from the multilayers after an intensive agitation. The UV-visible spectroscopy and atomic force microscopy measurements supported the improvement of the stability of the multilayers.

We develop a facile method to immobilize cucurbituril on silicon substrates through photochemical reaction with azido groups. Combining photolithography and the competitive molecular recognition between CB[7] and acridine orange base or 1-adamantanecarboxylic acid, a patterned surface with reversible fluorescence emission can be obtained.