REVIEW

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Interfacial Self-Assembly Nanostructures: Constructions

and Applications
Yanyan Li, Dingyitai Liang, Ruimin Wang, Shouzhi Yang, Wanshan Liu, Qi Sang, Jun Pu,
Yuning Wang,* and Kun Qian*

self-assembly.[11] Dip-pen nanolithog-

Interfacial self-assembly nanoarrays refer to the spontaneously organized raphy (DPN), a scanning-probe-based
nanostructures at interfaces, relying on the intrinsic properties of involved direct-write technique provides precise
materials, such as surface energy, molecular structure, and interactions. control of surface chemistry for creating
In recent years, the exponential growth of self-assembly nanotechnology surface-patterned chemical functionalities
at sub-100 nm scales, opening new possibil-
has substantially expanded the utility of nanomaterials. Particularly,
ities in molecular electronics, biomedicine,
non-covalent interactions-based interfacial self-assembly represents a viable and catalysis.[14] DPN enables the precise
and promising approach for the synthesis of novel nanostructure. This review fabrication of nanoarrays of biological
introduces the significance and current development status of interfacial molecules, such as DNA, proteins, and
self-assembly technology, focusing on the driving mode, application, viruses, facilitating advanced biological
studies, diagnostics, and localized sur-
and prospects of interfacial self-assembly nanoarrays over the past few years.
face reactions like DNA digestion and
polymerization.[15] Mirkin and colleagues
have reviewed the development and appli-
cation of DPN and soft etching techniques,
1. Introduction highlighting how DPN enables the direct transfer of molecules
In the past 30 years, nanomaterials, as a newly emerging mate- with nanoscale precision and flexibility in patterning.[16] How-
rial with active development, have gradually attracted the atten- ever, these approaches come with certain limitations and draw-
tion of academia and industry.[1–3] Ordered nanostructured units backs, including the need for special equipment and long pro-
have broad application prospects in the fields of magnetism, cessing times, as well as the challenges in proper functionaliza-
optics, electronics, and machinery due to their unique regu- tion and low throughput, which hinder their wide application.[17]
lar arrangement characteristics.[4–8] Nanostructures can be pro- Self-assembly as a captivating construction approach efficiently
duced in technical research laboratories through a variety of so- overcomes the challenges of top-down strategy to fabricate lo-
phisticated lithographic techniques, such as photolithography,[9] cally high-quality nanostructures for practical applications. It
electron beam lithography,[10] focused ion beam lithography, possesses the advantages of simplicity, low cost, and high produc-
soft lithography,[11] and nanoimprinting.[12] Limitations such as tion. Specifically, interfacial self-assembly enables small struc-
diffraction restrictions, high costs of facilities, and limited con- tural units to form various ordered pattern structures at multi-
trol over surface chemistry persist in traditional photolithogra- phase interfaces. These interfaces, as shared boundaries from
phy. Whitesides et al.[13] developed soft lithography techniques two or more separate components, play important roles in
capable of creating high-quality patterns and structures ranging mass and energy transfer. The components consist of organic
from 30 nm to 500 μm. The same group also highlighted inno- materials, such as polymer and carbon, or inorganic materi-
vative methods for nanostructure replication, including printing, als, including metals, metal oxides, silica, and semiconduc-
molding, embossing, near-field photolithography, and molecular tors. Goronzy et al. provided an overview of recent advances
in the field of supramolecular assemblies on surfaces, focus-
ing on self-assembled molecular networks. Different from clas-
Y. Li, D. Liang, R. Wang, S. Yang, W. Liu, Q. Sang, J. Pu, Y. Wang, K. Qian sical self-assembled monolayers, self-assembled molecular net-
State Key Laboratory of Systems Medicine for Cancer works are formed through weak physisorption and noncovalent
School of Biomedical Engineering and Institute of Medical Robotics
Division of Cardiology intermolecular forces, allowing for greater structural complex-
Renji Hospital, School of Medicine, Shanghai Jiao Tong University ity and tunability.[18] During molecular conversion at interfaces,
Shanghai 200030, P. R. China the interfacial dynamics determine the performance and proper-
E-mail: [email protected]; [email protected] ties of the materials, resulting in various structures. In the self-
Y. Li, D. Liang, R. Wang, S. Yang, W. Liu, Q. Sang, J. Pu, Y. Wang, K. Qian assembly procedure, the building blocks can be arranged into or-
Shanghai Jiao Tong University Sichuan Research Institute
Chengdu 610213, P. R. China
derly arrays through multiple driven forces, including van der
Waals forces,[19] electrostatic interactions,[20] hydrogen bonds,[21]
The ORCID identification number(s) for the author(s) of this article host-guest interactions,[22] magnetic fields,[23] etc. With the con-
can be found under https://doi.org/10.1002/smll.202405318 tinuous advancement of synthesis techniques, a series of lo-
DOI: 10.1002/smll.202405318 cally high-quality nanoarrays featuring controlled constituents

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Scheme 1. An overview of the construction methods and applications of interfacial self-assembly nanostructures.

and structures have been successfully fabricated using interfa- within a designated space, providing an effective method for
cial self-assembly methods.[24] Various nanostructures made up the controlled shaping of various materials. For instance, in-
of building blocks with different morphologies have been synthe- terfacial polymerization has been utilized to fabricate poly-
sized, including spheres, wires, rods, cubes, plates, polyhedrons, mer membranes, capsules, and nanofibers for applications in
etc.[25–28] drug delivery, nanofiltration, and chemical sensing.[32–35] Based
In the reviews involved with material self-assembly, few on the different interfaces, increasing efforts are being de-
have focused on the constructions and applications of in- voted to interfacial techniques for the construction of nanoarray
terfacial self-assembly nanostructures.[29,30] Herein, this structures.[35,36]
review provides a comprehensive overview of current re- For the liquid-solid interface, the layer-by-layer (LbL) assem-
search endeavors centered on interfacial self-assembly bly method is commonly used to integrate various materials
nanostructures, including their basic principles, construc- from liquid to solid surface, forming multilayer structures. Dur-
tion methods, and their applications across various domains ing LbL assembly, the involved reactive molecules are continu-
(Scheme 1). ously deposited onto a solid substrate, with a rinsing step per-
formed between each layer of deposition. Traditional LbL as-
2. Basic Principles of Self-Assembly at Interfaces sembly has been fundamentally important in developing mul-
tilayer composites made from hybrid organic-inorganic nanos-
Self-assembly is a simple and cost-effective process for fab- tructures. For example, Zhang et al.[37] discussed superhydropho-
ricating simple components into ordered structures, includ- bic hybrid films composed of silica nanoparticles (NPs) and
ing nanowires (NWs), nanotubes, and nanoarrays.[31] Specif- an ionic liquid, 1-dodecyl-3-methylimidazoliumbromide. In ad-
ically, interfacial self-assembly has attracted much attention dition to the ability to prepare multilayer films on flat sub-
due to the unique properties of multiphase interfaces, e.g., strates, LbL assembly can also prepare films on 3D substrates.
gas-liquid, liquid-liquid, solid-liquid, and gas-solid interfaces. For instance, Lin et al.[38] prepared nanoscale films with good
This approach enables the confinement of building blocks crystal structure, preferred direction, and accurately adjustable

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Figure 1. A) Schematic illustration of the LbL assembly method on a 3D substrate. Reproduced with permission.[38] Copyright 2021, John Willey and
Sons. B) Schematic illustration of self-assembly of Cu2 O NWs with controlled gaps using LB technology. Reproduced with permission.[39] Copyright 2023,
John Willey and Sons. C) Schematic illustration of the formation of plasmonic colloidosomes at liquid–liquid interface. Reproduced with permission.[51]
Copyright 2015, John Willey and Sons. D) Schematic illustration of the growth process of 2D-BN on SiO2 /Si. Reproduced with permission.[52] Copyright
2019, Springer Nature.

thickness on a TiO2 NWs array substrate using LbL assembly been produced using the liquid-liquid interfacial self-assembly
(Figure 1A). methods.[44,45]
For the gas-liquid interface, the Langmuir-Blodgett (LB) tech- For example, Girault and co-workers first reported an Au NPs
nique is an efficient method to fabricate various well-organized liquid mirror at the heptane/1,2-dichloroethane-water interface,
2D closely packed films. The LB technology enables the fabri- demonstrating high reflectance and electrical conductance.[46]
cation of a single-monomer thick organic film with controlled Zhang et al. fabricated a series of densely packed nanoar-
packing density. With this method, amphiphilic materials, dis- rays by self-assembly of plasmonic NPs at the oil-water inter-
solved in volatile substances and water, can move and form a face to quantify metabolites and biosamples.[22,47–50] Ling and
compact film on the air-water interface by tailoring the surface co-workers developed a plasmonic colloidosome system, that
pressure of the water. Feng et al.[39] reported a single-layer Cu2 O was 3D spherical microcapsules formed by the self-assembly
nanoarray prepared by self-assembly of Cu2 O NWs with con- of silver octahedra at the decane-water interface, for isolat-
trolled gaps using LB technology (Figure 1B). Baratto et al. fab- ing and monitoring analytes at ultra-trace level (<200 pL)
ricated a 2D nanoarray based on ZnO nanorod using the LB (Figure 1C).[51]
technique.[40] This technique shows great potential for creating The construction of gas-solid interfacial self-assembly nanos-
ultra-thin and highly-aligned nanoarrays. However, there remain tructures typically involves the secondary assembly of new com-
challenges in forming an insoluble monolayer of nanomaterials ponents on the surface of 2D materials, such as graphene (GR),
at the air-water interface, which limits the broader applications hexagonal boron nitride, transition metal dichalcogenides, etc.
of the LB technique.[30] These building blocks of 2D material can be combined to form
The liquid-liquid interface, as a straightforward and versatile vertically stacked LbL structures or laterally in-plane heterostruc-
technique, provides a significant platform for organizing vari- tures. Using techniques like chemical vapor deposition (CVD)
ous building blocks via the interfacial ordering effect.[17] It is or physical vapor deposition, 2D materials can be assembled on
considered the most flexible and versatile interface leading to a flat substrate. For instance, Liu et al. developed a catalyst-free
the development of numerous methods for assembling nano- and low-temperature method to grow uniform, polycrystalline 2D
materials into superstructures of varying sizes.[35] Early in the hexagonal boron nitride (2D-BN) directly on various substrates,
20th century, Ramsden[41] and Pickering[42] found that micron- including SiO2 /Si, quartz, sapphire, and even 3D patterned sur-
sized solid particles (e.g., Fe2 O3 and SiO2 ) could create solid-like faces by near-equilibrium plasma-enhanced CVD (Figure 1D).[52]
films at the boundary between two immiscible liquid phases.[43] Qian and colleagues fabricated a series of microarrays with gold
These systems, known as “Pickering emulsions”, illustrate the nanoshells on the surface using controlled particle synthesis, dip-
particle behaviors at the liquid-liquid interface, which promotes coating, and gold sputtering techniques.[53] Besides, alternative
the development of particle thermodynamics at interfaces. Since approaches beyond conventional methods have been explored.
the discovery of spontaneous adsorption at the liquid-liquid in- Deng and colleagues employed a “bottom-up” supramolecu-
terface in the 21st century, various 2D and 3D structures have lar assembly approach, utilizing the synergistic interactions

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between synthesized organic amphiphilic block copolymers (e.g., covalent interaction between noncharged molecules, plays a cru-
poly(ethylene oxide)-block-polystyrene) and silicotungstic acid to cial role in forming assembly structures.[57] Colloidal NPs in
assemble 3D tightly cross-linked composite nanowires at the gas- solution could organize into orderly packed structures on a
solid interface.[54] substrate or within a glass vial through solvent evaporation.
In the evaporation process, NPs could assemble via attractive
ligand-ligand interaction at a certain temperature or under dy-
3. Construction of Self-Assembly Interfacial namic vacuum conditions.[63–65] In this context, although the
Nanoarrays interparticle potential is attributed to a blend of different in-
teractions, van der Waals interaction serves as the main at-
The interfacial self-assembly strategy is an important bottom-
tractive component, effectively reducing electrostatic and steric
up constructing method for integrating nanoscale materials into
repulsion.
microscale structures through precise operation of solid-air-
The temperature and type of the solvent are the main fac-
liquid interfaces. In this bottom-up approach, individual building
tors that regulate the van der Waals interactions in the pro-
blocks or molecules are assembled into larger structures through
cess of interfacial self-assembly.[57] Hu et al. discussed the
self-organization processes, guided by their inherent properties
temperature-induced transformation of self-assembly phthalo-
and interactions. In a system at energy-efficient equilibrium, self-
cyanine molecular nanoarrays at the solid-liquid interface. By
assembly is driven by interactions among the NPs, such as van
controlling the substrate temperature, samples formed thermo-
der Waals forces, electrostatic interactions, etc.[55,56] These inter-
dynamically favorable nanoarrays with uniform shape and size
actions within NP self-assembly lead to novel collective proper-
by annealing at 323 K for 10 minutes.[66] Quan et al. reported
ties arising from synergistic effects among different function-
the self-assembly of ordered superlattices using different sol-
alized building blocks, such as efficient charge transfer, strong
vents. By exploring the translation and orientation characteris-
light absorption, etc., which are crucial for fabricating desirable
tics of these superstructures through transmission electron mi-
nanoarrays. Moreover, the anisotropic shapes of NPs and their in-
croscope (TEM) tomography and 3D reconstruction analysis, this
teractions contribute to the formation of nanoarrays with specific
study highlighted the importance of solvent selection in fine-
structures.[57]
tuning ligand-solvent interactions during self-assembly.[63] As
Enhancing the orderliness of assembled nanostructures has
shown in Figure 2A, a representative TEM image of the synthe-
been a primary focus of researchers. The ordered arrangement of
sized Pt nanocubes (Pt NCbs) indicated each NCbs was enclosed
nanostructures has been well fabricated by means of templating
by four equivalent (100) planes in the monolayer, with an aver-
techniques and non-template methods.[58,59] In the templating
age side length of 10 nm. Besides, Choueiri et al. prepared self-
techniques, the template as a scaffold contains active sites, which
assembly polyferrocenylsilane-functionalized AuNPs nanostruc-
are divided into hard templates (e.g., silica nanospheres and car-
tures with distinctive attributes, achieved through manipulating
bon nanotubes) and soft templates (e.g., surfactants and polymer
the interplay between polymer conceptual entropy and solvent
micelles), allowing for different particles deposition and arrange-
interactions.[67]
ment into a structure with a morphology. In the non-template-
Similarly, Oh et al. created highly ordered functional nanoar-
directed self-assembly process, intrinsic characteristics of parti-
rays through the binary self-assembly of conjugated block
cles play important roles, which are easily controlled by exter-
copolymers and quantum dots (QDs) at the air-water inter-
nal stimuli and fields. Multiple noncovalent interactions between
face, where the particles are assembled via van der Waals
particles such as van der Waals and Coulombic forces, facilitate
forces.[68] Lu et al.[69] prepared bifunctional ordered copper hy-
the self-assembly of building blocks into ordered structures.[58,60]
droxide/Au nanoarray composites using a microfluidic assisted
External stimuli (e.g., temperature, light, solvent polarity, ion
gas-liquid interface self-assembly method (Figure 2B). This com-
concentration, etc.) can provide additional control to modu-
posite material exhibits a large surface area and is suitable
late interparticle forces under equilibrium or nonequilibrium
for highly sensitive gas adsorption detection. Song et al. devel-
conditions.[31] Meanwhile, external fields (e.g., electric, magnetic,
oped a general-purpose technique for preparing interfacial self-
and flow field, etc.) have emerged as key methods to direct disor-
assembly films, enabling quick and efficient assembly of NP
dered suspension of particles into ordered structures. Besides,
monolayers based on intermolecular van der Waals forces. In
the importance of preparing nanoparticles with uniform size,
this method, a single-layer film was obtained by adjusting the
shape, and composition was highlighted as these are fundamen-
contact angle of the NPs, utilizing van der Waals forces for in-
tal units for the orderly assembly of nanostructures.[61] Specifi-
stantaneous and universal interfacial self-assembly, followed by
cally, larger-scale ordered complex structures can be formed from
coating onto different substrate surfaces via template transfer
disordered systems by exploiting non-equilibrium states, hid-
technology.[70]
den symmetries, and dissipative properties in the self-assembly
process.[62]
Herein, we provide a brief introduction to typical driving force-
based interfacial self-assembly nanostructures. 3.2. Electrostatic Interactions

Analogous to the van der Waals force, electrostatic interac-

3.1. Van der Waals Force tions significantly influence the dynamics of a system across
multiple scales. Different from van der Waals force, electro-
Typically, the self-assembly of NPs primarily occurs via non- static interactions cause oppositely charged particles to attract
covalent interactions. The van der Waals force, a key non- and like-charged particles to repel each other. Considering the

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Figure 2. A) TEM image and schematic of self-assembled Pt NCbs. Reproduced with permission.[63] Copyright 2014, American Chemical Society. B)
Schematic illustration of the fabrication route for Cu(OH)2 /Au/SiO2 nanoarray. Reproduced under the terms of the Creative Commons CC BY license.[69]
Copyright 2023, Multidisciplinary Digital Publishing Institute. C) Schematic illustration of the AuNP nanoarray. Reproduced with permission.[49] Copy-
right 2021, American Chemical Society. D) The preparation of GNs-CdS QDs hybrid films. Reproduced with permission.[75] Copyright 2014, American
Chemical Society.

surface charge-induced screening effects, electrostatic interac- The LbL assembly technique is generally used to fabricate
tions are sensitive to pH, electrolyte concentration, and ion multi-component films on solid supports by consecutive adsorp-
strength. In systems comprising oppositely charged NPs, binary tion of polyanions and polycations from solution.[76] Decher et al.
superstructures can be self-assembled by precisely controlling further fabricated highly anisotropic nanocomposite films us-
the NPs concentration, size, and the valence of surrounding ing spray-assisted alignment of silver nanowires through elec-
counter-ions.[71] During the interfacial self-assembly process, trostatic interaction. The alignment of the nanowires, quantified
NPs tend to migrate to the boundary layer to minimize interfa- by the nematic order parameter, can reach up to 0.98, indicat-
cial energy. The inherent electrostatic repulsion among charged ing that 97% of the nanowires are aligned within ± 15° of the
NPs allows for modulation of their spatial arrangement through spraying direction. The density of nanowires in the monolayer
Debye screening of the electrostatic repulsion by the ionic at- can be controlled by adjusting the spraying time, achieving up
mospheres within the electrolytes. The density of NP arrays is to 60% surface coverage. The optical properties of these aligned
determined by the balance between the adhesive forces binding nanowire films exhibited selective excitation of transverse and
NPs to the interface and their repulsive forces.[72] At present, longitudinal localized plasmon resonances. The polarization ef-
numerous nanoarrays are formed by electrostatic interactions. ficiency increases with nanowire density, degree of orientation,
For instance, Liu and co-workers[49] constructed noble metal and the number of layers.[77]
nanoarrays using oppositely charged colloidal particles as build-
ing blocks at the liquid-liquid interface (Figure 2C). The for-
mation of the closely packed arrays is attributed to the ratio 3.3. Hydrogen Bonds
of opposite charged NPs, appropriate electrolyte concentration,
and pH value to adjust the electrostatic attraction.[73,74] The con- Hydrogen bonds represent a distinct form of electrostatic dipole-
structed nanoarrays exhibit strong, tunable light-matter interac- dipole interaction occurring between a hydrogen donor and ac-
tions. Another example of self-assembled nanostructures driven ceptor, characterized by a directional and linear structure. These
by electrostatic interactions is a hybrid film of GR nanosheets bonds are essential molecular interactions that significantly con-
(GNs)-CdS QDs reported by Liu and co-workers.[75] A stable aque- tribute to the stability of substances. The strength of hydro-
ous dispersion of polymer-modified GNs was prepared by us- gen bonding between NPs is determined by the density of sur-
ing cationic poly(allylamine hydrochloride) (PAH) as a stabilizing face groups (─OH, ─COOH, or ─NH2 ). Research has exten-
agent to in situ reduce exfoliated graphite oxide. After sequential sively explored hydrogen bond-inducing self-assembly nanos-
assembly of the PAH-modified GNs (GNs-PAH) and negatively tructures, where hydrogen bonds between ligands attached to
charged CdS QDs, the GNs-CdS QDs hybrid films were formed NPs play a crucial role in facilitating the formation of 2D
via LbL self-assembly technique, where CdS QDs were uniformly structures.
distributed on the 2D GNs (Figure 2D). Compared to pure CdS Cai et al.[79] created a series of 2D plasmonic molecules
QDs and GNs films, these GNs-CdS QDs multilayered films ef- (PMs) via hydrogen-bond interactions between a pair of polymer-
ficiently enhanced the photoelectrochemical and photocatalytic modified AuNPs (hydrogen-bond donor and acceptor). As de-
activities under visible light irradiation. picted in Figure 3A, AuNPs were modified with a random

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Figure 3. A) Schematic illustration of the self-assembly of 2D PMs via hydrogen bond interaction. Reproduced with permission.[78] Copyright 2023, John
Wiley and Sons. B) Illustration of the multifunctional self-assembled AuNPs array fabrication at liquid-liquid interfaces. Reproduced with permission.[22]
Copyright 2023, John Wiley and Sons. C) Chemical structures of the designed NPSs and schematic representation of the photoresponsive NPSs at
the oil-water interface from the jammed state to the unjammed state. Reproduced with permission.[85] Copyright 2020, American Chemical Society. D)
Schematic representation and TEM image of the linear assembled Fe3 O4 NPs. Reproduced with permission.[89] Copyright 2013, John Wiley and Sons.
E) Schematic illustration of magnetic field-induced self-assembly of P3HT-b-PEG and IONPs at the air-water interface. Reproduced with permission.[90]
Copyright 2022, American Chemical Society.

copolymer of styrene and hydroxystyrene) as the hydrogen- 3.4. Host–Guest Interaction

bond donor, and polyethylene glycol (PEG) as the hydrogen-
bond acceptor. The coordination number of PMs was con- Due to the dynamic nature of host-guest interactions, vari-
trolled by the competition between polymer interactions and ous macrocyclic compounds have been widely chosen as host
solvation, leading to the self-assembly of 2D PMs through molecules to construct self-assembly nanostructures, such as pil-
adjustment of bonding strength using interacting solvents lar[n]arenes, cucurbit[n]urils (CB[n]), and cyclodextrins (CDs).
(tetrahydrofuran/CHCl3 ). Hou et al. developed a supramolecular CDs, as typical host molecules, can encapsulate a variety of
self-assembly strategy to construct amine-functionalized polyhe- small organic molecules through hydrophobic interactions. Vari-
dral oligomeric silsesquioxane forming a monolayer film at the ous supramolecular self-assembly structures and 2D nanoarrays
oil-water interface.[80,81] Intermolecular hydrogen bonds among based on CDs have been manipulated using host-guest interac-
surface ligands of NPs facilitate the formation of densely packed tions. For instance, Wang et al.[22] constructed self-assembled
2D structures, where multiple ultrathin films were formed Au nanoarrays at the liquid-liquid interface through host-guest
through interactions between ligand-capped AuNPs via hydro- interactions between 𝛽-CD and aromatic groups. Simultane-
gen bonding. AuNPs functionalized with mercaptoundecanoic ously, these Au nanoarrays could enrich aromatic amino acids
acid could self-assemble along poly(ethylene oxide) chains due to for direct analysis with high sensitivity and selectivity, as de-
the hydrogen bonding occurring between the carboxylic groups picted in Figure 3B. Fang et al.[84] fabricated multifunctional
of mercaptoundecanoic acid and the ether oxygen atoms of AuNP arrays with tunable optical properties by utilizing host-
poly(ethylene oxide).[82] During hydrogen bond-inducing self- guest interactions between 𝛽-CD ligands of AuNPs and poly(2-
assembly, pH value influences the formation of hydrogen bond- (dimethylamino)ethyl methacrylate) polymer brushes.
ing, with deprotonated acids in high pH unable to form hydrogen Shi and co-workers developed a photoresponsive NP sur-
bonds.[83,84] factant (NPS) at the water-oil interface by self-assembly of

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𝛼-CD modified AuNPs (𝛼-CD AuNPs) in the aqueous phase 4. Application of Interfacial Self-Assembly
and azo-terminated polymeric ligands (polystyrene (Azo-PS) Nanostructures
and poly-L-lactide (Azo-PLLA)) in the oil phase through host-
guest interaction, as illustrated in Figure 3C. Molecular recog- Self-assembly nanostructures exhibit unique optical, electronic,
nition between 𝛼-CD and Azo end-groups at the oil-water and magnetic properties, stemming from both individual build-
interface induced a reduction in interfacial tension, result- ing block characteristics and collective behaviors. This charac-
ing in the formation of a monolayer of NPs. Upon ex- teristic opens up new opportunities for a variety of applications,
posure to UV light, the trans-Azo-PLLA photoisomerizes to such as optical biosensing, electronic devices, energy conversion
cis-Azo-PLLA, enabling reversible manipulation of the NPSs nanodevices, etc.[91]
between jamming (solid-like) and unjamming (liquid-like)
states.[85]
In addition, Pfeffermann et al.[86] fabricated a large and 4.1. Surface-Enhanced Raman Scattering (SERS)
homogeneous 2D supramolecular polymeric film through
supramolecular polymerization at interfaces. At the water- SERS is a noninvasive spectroscopic sensing technique that
toluene interface, a true derivative in toluene and a naph- has been widely employed in analytical fields for decades.
thalene diimide derivative along with CB[8] in water were SERS provides molecular fingerprint information, offering ad-
assembled inside CB[8] via a host-guest enhanced donor- vantages such as high sensitivity (down to the single-molecule
acceptor interaction, resulting in the formation of highly ordered level), narrow spectral bandwidths, and straightforward sample
structures. preparation.[92–94] The enhancement in SERS primarily arises
from a strong electromagnetic field generated by metallic nanos-
tructures with small nanogaps, known as hotspots. Therefore,
3.5. Magnetic Field fabricating reliable, reproducible, and cost-effective SERS sub-
strates is crucial to enhance SERS sensitivity for various chemical
Under an external magnetic field, magnetic particles dis- and biosensing applications.
persed in oil or water become magnetized and naturally align Recently, various interfacial self-assembly NP arrays have been
with the orientation of the magnetic dipoles. Driven by mag- developed for use in SERS sensors. These self-assembled metal
netic fields, magnetic NPs such as Fe3 O4 , Ni, Co, or hy- NPs create abundant hotspots through plasmonic coupling be-
brid NPs with a magnetic component, can self-assemble into tween adjacent NPs, which efficiently improves the enhancement
nanostructures.[87] During the self-assembly of magnetic NPs, factor (EF). Cecchini et al.[95] prepared self-assembled Au nanoar-
multiple interactions (e.g., van der Waals forces, magnetic rays at the liquid-liquid interface as SERS platforms for moni-
dipole-dipole interactions, etc.) must be carefully balanced and toring trace analytes in multiphase systems. The density of the
considered. nanoarrays was controlled by varying the NP functionality, solu-
Singh et al. applied an external magnetic field to construct tion pH, and salt concentration. As depicted in Figure 4A, the NP
self-assembled NP monolayers over diethylene glycol, form- film formed at the oil-water interface by shaking the two phases
ing helical superstructures through the interplay of van der containing NPs and analytes. During this process, the distance
Waals forces, magnetic dipole-dipole interactions, Zeeman cou- between NPs decreased, allowing the NPs to capture analytes
pling, and entropic forces.[23] Taheri et al. employed a com- for trace analysis. Similarly, Zhou et al. presented a 2D interfa-
parable method for the self-assembly of iron oxide NPs, re- cial SERS platform based on AuNPs for capturing and detecting
sulting in 1D nano-chains, 2D monolayer sheets, and large trace levels of epinephrine in serum.[96] Wu et al. reported a re-
3D cuboids with internal ordering organization directed by producible and highly sensitive SERS substrate based on butanol-
an external magnetic field.[88] Specifically, this magnetic field- drived self-assembly of AuNPs for rapid diagnosis of severe acute
directed self-assembly method enabled the construction of respiratory syndrome coronavirus 2 (SARS-CoV-2). The butanol-
iron oxide nanocubes with a small size (≈8.2 nm), leverag- drived self-assembly process is shown in Figure 4B, where an
ing dipole-dipole interactions among small superparamagnetic aqueous droplet containing AuNPs and target DNAs was added
particles. to a butanol droplet. The butanol-drived dehydration enabled the
As shown in Figure 3D, Chong et al. demonstrated the linear loading of target DNAs onto the surface of AuNPs, forming a uni-
assembly of Fe3 O4 NPs, which were protected by a silica shell form SERS substrate with multiple hotspots. This substrate was
to enhance mechanical robustness and chemical resistance.[89] used in SARS-CoV-2 assays with a low limit of detection (LOD)
Park et al.[90] produced macroscopically ordered polymer films of 3.1 × 10−15 M.[97] Tian et al.[50] developed plasmonic metallic
with nanoscale properties through magnetic field-induced self- nanoarrays via an electrostatically driven self-assembly method
assembly of conjugated block copolymers, specifically poly(3- at liquid-liquid interfaces, demonstrating high SERS sensitivity
hexylthiophene)-block-polyethylene glycol (P3HT-b-PEG), and at the femtomole level, along with good reproducibility and sta-
iron oxide NPs at the air-water interface (Figure 3E). This study bility. The substrates were functionalized with concanavalin A
highlighted that magnetic interactions significantly enhanced the for capturing and label-free detection of eight different bacterial
degree of ordering, resulting in a long-range ordered nanoarray species (both Gram-positive and Gram-negative bacteria) at the
of P3HT-b-PEG and iron oxide NPs (IONPs). Magnetic dipole in- single-cell level.
teractions drove the self-assembly process by forming intermedi- Feng et al.[39] reported a Cu2 O nanoarray by self-assembly of
ate magnetic subunits, which were then arranged into long-range Cu2 O NWs as SERS substrate for highly selective identification
ordered structures due to magnetic forces. of biological species in complex biological systems (Figure 4C).

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Figure 4. A) Schematic illustration of liquid-liquid interfacial assembled NP for detection of malachite green isothiocyanate. Reproduced with
permission.[95] Copyright 2012, Springer Nature. B) Schematic illustration of the butanol-drived self-assembly process of AuNPs. Reproduced with
permission.[97] Copyright 2023, American Chemical Society. C) Schematic illustration of fabrication and Raman enhancement of Cu2 O nanoarray with
adjustable gaps. Reproduced with permission.[39] Copyright 2023, John Wiley and Sons. D) Schematic illustration of 3D hybrid SERS substrate self-
assembly. Reproduced with permission.[98] Copyright 2022, American Chemical Society.

The designed Cu2 O nanoarray exhibited excellent SERS activities 4.2. Matrix-Assisted Laser Desorption Ionization Mass
with a high EF of 3.19 × 1010 , enabling rapid and sensitively de- Spectrometry (MALDI-MS)
tect SARS-CoV-2 RNA with a LOD of 60 copies mL−1 in 5 min.
Fu et al. prepared a bifunctional 3D hybrid substrate at an air- MALDI-MS has been widely adopted in bioanalysis for its abil-
water interface using the LbL technique combined with the in- ity to provide accurate molecular information. Over the past
ternal standard (IS) strategy (Figure 4D). The substrate included decade, numerous nanostructures have been developed as matri-
the bottom Au@IS@SiO2 monolayer as the calibration unit and ces to assist in LDI-MS analysis of small molecules. These nanos-
the top Au octahedron monolayer as the detection unit. The 3D tructures exhibit unique optical and electronic properties, effec-
hybrid nanostructure largely improved the SERS performance in tively enhancing the performance of LDI-MS by reducing back-
SERS intensity and reproducibility, owing to the calibration unit, ground signals compared to traditional organic matrices.[99,100]
which was applied to detect cotinine and creatinine in complex However, the non-uniform distribution of analytes on nanostruc-
samples.[98] tures often leads to poor reproducibility of MS signals, which

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Figure 5. A) Schematic illustration of self-assembled hyperbranched Au nanoarray-based LDI-MS platform for early-stage diagnosis of renal carcinoma.
Reproduced with permission.[102] Copyright 2024, American Chemical Society. B) Schematic illustration of NGQD@MoS2 /SiNWs nanostructure for MS
imaging. Reproduced with permission.[103] Copyright 2022, American Chemical Society.

significantly impacts quantitative analysis. Therefore, fabricating 4.3. Catalysis

uniform nanostructures as LDI-MS substrates is crucial to en-
sure accuracy. The periodic nanostructured arrays have been applied in opto-
Rotello and colleagues developed a MoS2 thin film by LbL electronic and catalysis fields, such as large surface-to-volume
technique as an efficient platform for LDI-MS analysis of small ratio and good light-absorption ability. For instance, metal NPs
molecules.[101] The MoS2 nanoflakes were immobilized on a (Au, Ag, Pt, Pd, etc.) present excellent catalytic activities. How-
chemically functionalized substrate using LbL assembly with ever, these colloidal metal NPs are easy to aggregate due to high
polyallylamine hydrochloride to create a chip-based LDI-MS surface energy, resulting in reduced activity. Thus, the immobi-
platform. By controlling the number of LbL assembly cycles, lization of metal NPs catalysts is significant for efficient catalysis.
the (MoS2 nanoflake)n films-based LDI-MS efficiency was opti- To further improve the performance, Sun et al. reported a peri-
mized. Among the different configurations, the optimized (MoS2 odic Au array on silicon wafers as electrodes to catalyze and de-
nanoflake)3 film demonstrated the highest LDI-MS efficiency, su- tect H2 O2 using the electrochemical approach, which possessed
perior salt tolerance, reusability, and uniform ion signal distribu- the advantage of high stability, sensitivity, and reproducibility.[104]
tion. Zhou et al. fabricated heterogeneous catalysts by self-assembly of
Wang et al.[102] fabricated series of closely packed Au nanoar- Au@Ag@polydopamine (PDA) core-shell bimetallic NPs into a
ray at oil-water interface as LDI-MS substrates by self-assembly monolayer at the oil-water interface and transferred them to solid
of AuNPs with different morphology and modification. The Au substrates (Figure 6A). The nanocatalysts with a closely packed
nanoarrays presented strong electromagnetic field enhancement array showed excellent catalytic activity and stability in a typical
and excellent optical thermal conversion ability, enabling the im- reduction model of 4-nitrophenol to 4-aminopheol by NaBH4 .[105]
provement of the LDI efficiency for small molecule analysis. Since the photoelectrochemical (PEC) water splitting was re-
Specifically, the anisotropic-shaped AuNP-based nanoarray gen- ported by Fujishima and Honda in 1972, plenty of semicon-
erated more hotspots for enhancing the electromagnetic field, ductors have been applied to photocatalysis in various fields,
which further amplified the MS signal. Meanwhile, the inter- such as water splitting, carbon dioxide reduction, etc.[106] Cur-
facial self-assembled nanoarray with a homogeneous structure rently, the metal oxide semiconductors (e.g., ZnO, TiO2 ) based
highly improved the reproducibility of the MS signal for accu- hybrid photocatalysts have attracted attention in photoelectro-
rate quantitative analysis. As shown in Figure 5A, the Au nanoar- chemistry. To obtain excellent PEC performance, it is impor-
rays are successfully applied in accurate quantitation of spe- tant to fabricate photoelectrode nanofilm with well-defined lay-
cific metabolites, such as glucose, for disease monitoring and ers and thickness. Compared to the traditional dropping or spin-
profiling of metabolic fingerprints from biofluids, such as cere- coating approach, self-assembly strategies have been used to con-
brospinal fluid, serum, and urine, toward early-stage diagnosis struct uniform films for photocatalysis in recent years. Sun et al.
of tumors. fabricated densely packed Au@ZnO NP arrays using a facile
Liu et al. developed a nitrogen-doped graphene quantum dot and effective organic solution-assisted interfacial self-assembly
(NGQD)@MoS2 /SiNWs nanostructure for MS imaging of phos- method (Figure 6B). After transferring it onto indium-tin-oxide
pholipids on non-small cell lung cancer tissue (Figure 5B). For substrates, the Au@ZnO NP array films were used for PEC water
the synthesis of NGQD@MoS2 /SiNWs hybrid nanostructure, splitting, exhibiting good behavior with the photocurrent density
the prepared NGQD@MoS2 nanoflakes with negative charges of ≈3.08 mA cm−2 at 0.4 V.[107]
were self-assembled on the top of positive charged SiNWs via Huang et al. constructed an over 3D CdSe QDs-GR nanocom-
electrostatic interaction. The substrate presented enhanced LDI posites by LbL self-assembly of negatively charged CdSe QDs
efficiency and molecule imaging capability for lipid analysis on and GR nanosheets with positive charge via electrostatic inter-
the tissue.[103] action. Such nanocomposites exceeded the original CdSe QDs,

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Figure 6. A) Schematic illustration of synthesis and interfacial self-assembly of core-shell Au@Ag@PDA NPs and application in recyclable nanocatalysts.
Reproduced with permission.[105] Copyright 2013, John Wiley and Sons. B) The fabrication of the Au@ZnO NP array as an electrode for PEC water
splitting. Reproduced with permission.[107] Copyright 2017, American Chemical Society. C)The fabrication of fluorescent sensing film assembled on the
surface of the micropatterned ionic liquid. Solid substrate: Au-coated silicon substrate. Reproduced with permission.[114] Copyright 2022, American
Chemical Society.

efficiently improving the photoredox capabilities, and exhibit- of the AuNPs reduced Hg2+ forming gold amalgam, which en-
ing multifunction toward selective oxidation of aromatic alcohols hanced the catalytic ability of AuNPs and generated varying de-
to aldehydes and selective reduction of nitroaromatics to amino grees of color variation for sensitive detection of Hg2+ with LOD
compounds when exposed to visible light.[108] of 0.021 nm.[110]
The 2D plasmonic periodic arrays have proven to be valuable
in applications of surface plasmon resonance (SPR) sensors. For
4.4. Other Sensors example, monolayer colloidal crystals (MCCs) as ordered arrays
of nanoscale SiO2 present advantages in SPR sensors. The high-
Numerous studies have reported AuNPs-based colorimetric sen- quality MCCs with small surface roughness offer great plasmonic
sors for visual detection without the need for labeling, owing performances, possessing the ability to confine the light energy
to their optical characteristics.[109] Nevertheless, the cross-linked into nanometer size to generate strong local field enhancement
AuNPs in a solution tend to aggregate, resulting in an unstable and to reduce the additional scattering and absorption losses.
signal. Considering that, Liu et al. fabricated 2D self-assembly To achieve practical application, it is necessary to fabricate large-
AuNP sheets at an oil-water interface for colorimetric sensing of scale and high-quality MCCs with high performance in sensitiv-
Hg2+ . Such 2D spatial packed nanoarray avoided chaotic arrange- ity and reproducibility. Wang et al. designed an orderly arranged
ment of the AuNPs in 3D space and improved the catalytic abil- hexagonal MCCs array using an interfacial capillary-force-driven
ity, achieving catalysis of 3,3′,5,5′-tetramethylbenzidine (TMB) self-assembly strategy. The MCCs-based SPR sensor achieved an
and H2 O2 to oxTMB. In the presence of Hg2+ , the citrate ions excellent refractive index sensitivity value of 3497 nm RIU−1 ,

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and ultrasensitive detection of bovine serum albumin at 10−8 M. the equilibrium ordered ones. Therefore, it is challenging to
Based on the obtained MCCs array, more large-scale nanostruc- overcome the high energy barrier of the trapped entangled state
ture arrays could be built for extensive applications.[111] within the least time.
Fluorescent films have been regarded as powerful tools for on- On the other, large-area orderly arrangements remain
site and in situ detection of trace analytes in various fields, in- a significant challenge in constructing interfacial-ordered
cluding drugs, volatile organic compounds, and toxic and haz- nanostructures.[115–117] The cost and efficiency in scale-up and
ardous chemicals, etc. The fluorescent film-based sensors pos- mass production of interfacial self-assembly nanoarrays need
sess the features of small size, low cost, easy operation, high sen- to be considered for practical applications. Significant research
sitivity, and fast response time. Fluorescence sensing requires efforts have been devoted to achieving larger areas of ordered
complete contact and interaction between the fluorescent unit nanostructures. Techniques involving external fields, such as
and the analyte molecule.[112] To obtain excellent sensing perfor- electric and magnetic fields, as well as templating methods
mance, it is crucial to fabricate suitable film to ensure an effective utilizing soft and hard templates, have been proven effective
interaction. Liu et al. developed a nanofilm at an air/liquid inter- in improving the orderliness of assembled nanostructures. For
face by using a fluorescent o-carborane derivative and a cross- example, the electric-field-assisted assembly method has been
linker trihydrazides as a building block. Due to the great poros- applied to assemble nanomaterials without dimension limits,
ity of the nanofilm, the analyte could be bound and transferred which provides a platform with substantial commercial value
for visualization-based qualitative sensing. The fluorescence film for the fabrication of high-performance devices at an indus-
sensor realized highly efficient detection of ethephon in the vapor trial scale.[118] Yu’s group developed a bottom-up directional
phase with LOD <0.2 ppb and a response time <10 s.[113] freezing method using ice templating to synthesize a class of
Lei et al. developed an innovative fluorescent film through the inorganic large nanosheets with a lateral scale of up to several
self-assembly of amphiphilic boron-dipyrromethene derivatives millimeters.[119]
on a micropatterned ionic liquid surface (Figure 6C). Compared In the forward development, researchers should devote efforts
to solid-state films, these monolayer films demonstrated a simi- to addressing these challenges to further revolutionize the in-
lar photochemical stability to that of a solution. Additionally, the terfacial self-assembly fields. Future studies are expected to ex-
interfacial assembly process avoided the fluorophores diffusing, plore novel construction methods and expand new applications,
which significantly improved the sensing performance with ex- contributing to nanotechnology development and significant ad-
cellent photochemical stability. The fluorescence sensing films vancements in human society.
achieved rapid detection of diethylchlorophosphate (DCP) vapor
with high sensitivity and selectivity.[114]
Acknowledgements
5. Conclusion and Perspectives This work was financially supported by NSFC (22204103, 82421001),
MOST (2022YFC2502800), Medical-Engineering Joint Funds of Shang-
In summary, the interfacial self-assembly nanoarrays have
hai Jiao Tong University (YG2021ZD09, YG2023QNA12, YG2023ZD08,
demonstrated a remarkable capacity for precise fabrication of YG2024ZD07), Shanghai Jiao Tong University Inner Mongolia Research
complex nanostructures, enabling the tailoring of material prop- Institute (2022XYJG0001-01-16), Sichuan Science and Technology Pro-
erties to suit a wide range of applications. Activated by various gram (2024YFHZ0176), Innovative Research Team of High-Level Local
driving forces, including van der Waals interactions, electrostatic Universities in Shanghai (SHSMU-ZDCX20210700), and Project 2021-
attractions, hydrogen bonding, host-guest interactions, and mag- 01-07-00-02-E00083 by Shanghai Institutions of Higher Learning. This
work was also sponsored by the Science and Technology Commission of
netic fields, the building blocks are capable of self-assembly into
Shanghai Municipality (2021SHZDZX, 20DZ2220400), and the Innovation
diverse nanostructures, which largely provides the possibility for Group Project of Shanghai Municipal Health Commission (2022JC013,
the design of functional materials with distinctive optical, elec- 2019CXJQ03).
trical, and mechanical characteristics. Until now, the interfacial
self-assembly nanoarrays have been widely used in various fields,
such as SERS, MS, fluorescence, catalysis, and others. Conflict of Interest
Despite the significant progress made in the field, the interfa-
cial self-assembly technique is still facing challenges. On the one The authors declare no conflict of interest.
hand, the precise control and optimization of the self-assembly
nanostructure remain complicated and need a deeper under-
standing of the mechanisms of interfacial interactions and self- Keywords
assembly processes. Different from macroscopic systems, the
interfaces, nanofilm, nanostructure, self-assembly, sensor
self-assembly process at the micro-nano scale inherently exhib-
ited randomness, making modeling and control difficult. Dur-
Received: June 28, 2024
ing the self-assembly of nanomaterials, the driven forces and
Revised: September 5, 2024
factors are multiple, making it challenging to understand and Published online: September 20, 2024
control specific factors for optimization. Meanwhile, the lack of
metrology is a major challenge in the real-time measurement
and manipulation of these small-scale systems. Additionally, self-
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Yanyan Li received her B.S./M.S. in biomedical engineering from Sichuan University. She is currently
studying for a Ph.D. at the School of Biomedical Engineering, Shanghai Jiao Tong University, under the
supervision of Prof. Kun Qian. Her current research is focused on the development of novel nanode-
vices for in vitro diagnostics.

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Yuning Wang received her Ph.D. in analytical chemistry from Fudan University. Currently, she is an
assistant professor at the School of Biomedical Engineering, at Shanghai Jiao Tong University. Her
research interests focus on the development of novel signal amplification methods based on mass
spectrometry for biomolecule detection.

Kun Qian received his B.S./M.S. from Fudan University, his Ph.D. from the University of Queensland,
and held the position of research fellow at Stanford University. He is now a principal investigator
(PI) and distinguished professor at the School of Biomedical Engineering and School of Medicine,
Shanghai Jiao Tong University. His research interests and efforts are on design, synthesis, engineer-
ing, and advanced biomedical applications of materials and devices. His group aims at the develop-
ment and commercialization of bioanalytical methods and mass spectrometry techniques for diverse
biomolecules in biomedical fields.

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