Superhydrophobic Surface-Assisted Preparation of Microspheres and Supraparticles and Their Applications

Superhydrophobic surface(SHS) has been well developed, as SHS renders the property of minimizing the water/solid contact interface. Water droplets deposited onto SHS with contact angles exceeding 150°, allow them to retain spherical shapes, and the low adhesion of SHS facilitates easy droplet collection when tilting the substrate. These characteristics make SHS suitable for a wide range of applications. One particularly promising application is the fabrication of microsphere and supraparticle materials. SHS offers a distinct advantage as a universal platform capable of providing customized services for a variety of microspheres and supraparticles. In this review, an overview of the strategies for fabricating microspheres and supraparticles with the aid of SHS, including cross-linking process, polymer melting,and droplet template evaporation methods, is first presented. Then, the applications of microspheres and supraparticles formed onto SHS are discussed in detail, for example, fabricating photonic devices with controllable structures and tunable structural colors, acting as catalysts with emerging or synergetic properties, being integrated into the biomedical field to construct the devices with different medicinal purposes, being utilized for inducing protein crystallization and detecting trace amounts of analytes. Finally,the perspective on future developments involved with this research field is given, along with some obstacles and opportunities.

Cross-scale modulation for aqueous fabrication of monodisperse Cu2−xE(E=S,Se,Te)nanocrystals and supraparticles

Exploring aqueous nano-fabrication with monodisperse and hierarchical characteristics is fundamentally and technically significant.Herein,we discover that inter-particle nano–nano scale interactions profoundly affect the products’morphology ranging from polydisperse→monodisperse to individual→hierarchical manipulation.Accordingly,we present a“nucleationgrowth-dispersion triple modulation”strategy for fabricating monodisperse Cu2−xE(E=S,Se,Te)nanocrystals(NCs)and supraparticles(SPs).Such full-process and cross-scale control is conducted by two rationally selected ligands(cysteine and citrate molecules),which are responsible for atom/molecule–nano and nano–nano interaction modulations,respectively.Cysteine reacts with the cations and forms low reactive(cysteine-Cu+)n coordination polymers,which overcomes the commonly concerned nucleation and particle growth induced polydispersity.Citrate,by virtue of its strong negative charge modulated NC–NC interactions,decides the products morphology from polydisperse products to monodisperse NCs to monodisperse hierarchical SPs.These findings not only present new insights into aqueous nano-synthesis chemistry but provide an eco-friendly system for versatile and high-quality nano-entity fabrication.

Dynamic supraparticles for the treatment of age-related diseases

Age-related diseases(ARDs) are arising as a major threat to public health in our fast-aging society.Current development of nanomedicine has sparked much optimism toward ARDs management by improving drug delivery and controlled drug release. However, effective treatments for ARDs, such as cancer and Alzheimer’s diseases(AD), are still lacking, due to the complicated pathological features of ARDs including multifactorial pathogenesis, intricate disease microenvironment, and dynamic symptom manifestation. Recently, dynamic supraparticles(DS), which are reversibly self-assembled functional nanoparticles, have provided a novel strategy for combating ARDs. Besides the intrinsic advantages of nanomedicine including multifunctional and multitarget, DS are capable of dynamic structural reconfiguration upon certain stimulation, creating another layer of maneuverability that allows programmed response to the spatiotemporal alterations of ARDs during progression and treatment. In this review,we will overview the challenges faced by ARDs management, and discuss the unique opportunities brought by DS. Then, we will summarize the designed synthesis of DS for ARDs treatment. Finally, we will dissect the therapeutic targets in ARDs that can be exploited by DS, and present the encouraging advances in this field. Hopefully, this review will bridge our knowledge of the design principle of DS and ARDs management, which may inspire the future development of potent theranostic agents to improve the healthcare.

Hybrid supraparticles of carbon dots/porphyrin for multifunctional tongue-mimic sensors

Supraparticles(SPs),such as assembly of inorganic components with organic,have made tremendous attention in biochemical analysis,which represents a novel but challenging research orientation.Herein,a single-SPs multifunctional fluorescent sensor array has been developed for high-throughput detection of heavy metal ions in biofluids,which is based on an inorganic/organic hybrid SPs consisting of carbon dots(CDs)and an easily available porphyrin[5,10,15,20-tetra(4-carboxyphenyl)porphyrin(TCPP)].TCPP can aggregate with the CDs to form the assembly(CDs/TCPP SPs)through the electrostatic andπ-πstacking interaction.There are two independent and clearly separated fluorescence emission peaks at 470 and 668 nm in the resultant CDs/TCPP SPs under 380 nm excitation.As a proof-of concept design,F 470,F 668,F 668/F 470 of SPs are chosen as three sensor components to constitute our sensor array.With the addi-tion of metal ions,three sensor components can generate different fluorescence response patterns for discriminating 11 heavy metal ions via principal component analysis(PCA).Additionally,thiols can read-ily capture Cu^(2+)to switch the fluorescence of CDs/TCPP initially altered by Cu^(2+).Hence,CDs/TCPP-Cu^(2+)ensemble is further demonstrated to be a powerful sensor array for pattern recognition of 7 thiols and even chiral recognition of cysteine enantiomers.This novel strategy avoids the tanglesome synthesis of multiple sensing probes and dedicates an innovative method for the facile establishment of tongue-mimic sensors,which would prospectively sprout more homologous assumptions to broaden its application toward more biosensing fields.

Fluorescent Cadmium Sulfide Supraparticles: One-Step In situ Self-Assembly Fabrication and Cationic Surfactant Chain Length-Dependent Mitochondria Targeting Capacity

The exploration of novel fluorescent tools for subcellular analysis is of great importance for both chemical biology and biomedicine.Herein,we present an in situ self-assembly strategy for fabricating fluorescent and monodisperse Cd S supraparticles(SPs),which are subsequently employed for mitochondria targeting applications.Using bovine serum albumin and linear chain cationic surfactants as templates and electrostatic modulators,respectively,Cd S SPs can be well fabricated by the proposed one-step self-assembly approach in aqueous medium.In addition to high stability,favorable biocompatibility,as well as decent quantum efficiency,the as-prepared SPs have mitochondria targeting capacity due to their cationic surfactant modification.Interestingly,the localization capacity is positively correlated with the length of the cationic surfactant molecules.As the carbon chains of the cationic surfactant molecules enhance from 10 to 16 atoms,the colocalization efficiencies are correspondingly increased from 81 to 84%.

Chiral Cu_(x)Co_(y)S Supraparticles Ameliorate Parkinson’s Disease

Protein aggregation causes alpha-synuclein(α-syn)to change from its original physiological role to a pathological state,which is a potential pathogenic mechanism in Parkinson’s disease(PD).Chiral _(L/D)-Cu_(x)Co_(y)S supraparticles(_(L/D)-SPs)with a circular dichroism value of 35 mdeg at 805 nm were fabricated using a simple wet-chemical method.The _(L/D)-SPs prevented the α-syn monomers from forming fibrils and triggered the α-syn fibrils to turn into monomers under 808 nm near-infrared(NIR)light.In living MN9D cells,D-SPs reduced cellular damage,neuronal functional deficits,and neuron loss caused by α-syn fibrils after NIR spectroscopy treatment within 10 min to prevent α-syn aggregation.Significantly,the reactive oxygen species produced by _(D)-SPs were 1.42 times higher than those produced by _(L)-SPs.In vivo experiments showed that _(D)-SPs had a protective effect on neuron damage caused by α-syn aggregate deposition,reduced the symptoms in a mouse model of PD,and restored cognitive ability.After NIR light treatment,the amount of α-syn in a mouse model of PD decreased by more than 67.5%.At the same time,_(D)-SPs gradually decomposed into small nanoparticleswithin 60 days and were excreted through the blood-brain barrier.This discovery paves theway for the treatment of neurodegenerative diseases using chiral SPs under NIR light irradiation.

Multi-chambered,carbon-coated Ni_(0.4)Fe_(2.6)O_(4) nanoparticle superlattice microspheres for boosting water oxidation reaction

Developing active and robust non-noble-metal-based electrocatalysts for the oxygen evolution reaction(OER)is of vital practical significance for accelerating the kinetics of water splitting.Here,a novel double emulsion template method is proposed to design and prepare hierarchically multichambered,carbon-coated Ni_(0.4)Fe_(2.6)O_(4) nanoparticle superlattice microspheres(M-NFO@C-NSMs)for the highly efficient oxygen evolution.The high-temperature calcination under inert gas enables an improved electrochemical property by rationally transforming the long-chain organic capping ligands into partially graphitized uniform carbon coatings.More importantly,benefiting from the unique hierarchical superstructure with macro-/meso-/microporosities and three-dimensional continuous conductive carbon frameworks,M-NFO@C-NSMs exhibit comprehensively enhanced OER activity in a dilute alkaline electrolyte as compared to their solid counterparts and most spinelbased electrocatalysts reported to date.Notably,the collective property of supraparticles endowed M-NFO@C-NSMs with superior long-term cyclic stability.This work sheds light on the sophisticated design of functionalized supraparticles for efficient water splitting.