Lignin-assisted construction of sub-10 nm supramolecular self-assembly for photothermal immunotherapy and potentiating anti-PD-1 therapy against primary and distant breast tumors

Photothermal therapy(PTT)has brought hope for cancer treatments,with hyperthermia-induced immunogenic cell death(ICD),which is a critical part of therapeutically induced antitumor immune responses.Limited immune stimulation response in PTT is the primary reason for incomplete tumor ablation,therefore demonstrating urgent requirements for ICD amplifier.Herein,a sub-10 nm supramolecular nanoassembly was formed by coassembly of clinically approved aluminum adjuvant and commonly used indocyanine green(ICG)under the assistance of lignosulfonate(LS,a green and sustainable multifunctional lignin derivative)for localized photothermal-immunotherapy of breast cancer.The overall results revealed that LS-Al-ICG is capable of inducing amplified ICD,efficiently eliciting solid immune responses through dendritic cells(DCs)activation and cytotoxic T-cell responses initiation for tumor killing.Moreover,anti-PD-1 therapy blocked the PD-1 pathway and led to remarkable anti-tumor efficacy against laser-irradiated primary tumors and distant tumors by potentiating systemic tumor specific T cell immunity.The results of this study demonstrate a handy and extensible approach for engineering green natural lignin nanoparticles for cancer immunotherapy,which shows promise for delivering other therapeutics in biomedical applications.

Supramolecular Self-assembly and Functionalization of Porphyrin-based Systems

Porphyrins are abundant in nature. They have been frequently employed as building blocks in the construction of nanoarchitectures and functional supramolecular systems. Recently, a series of novel porphyrin molecules including small molecules and polymers have been originally designed and synthesized with the aim of producing nanostructures with controllable-growth and materials with high-performance. Literature coverage is through 2004-2012. This review gives a full summary of related studies in our group.

Supramolecular Self-assembly Formed from Cucurbit[8]uril and p-Hydroxybenzoic Acid

The binding behavior of cucurbit[8]uril(Q[8])and p-hydroxybenzoic acid(p-HBA)has been investigated using ^(1)H NMR titration experiments,UV-Vis absorption,isothermal titration calorimetry(ITC),and X-ray crystallography.Results revealed that the Q[8]can accommodate two p-HBA molecules to form a 1:2 host-guest inclusion complex in solution,namely(p-HBA)2@Q[8].From a poorly scattering crystal,we were able to identify two symmetry unique Q[8]rings,but with different p-HBA fillings.The structure can be represented as Q[8]+1.5 p-HBA,which gives Q[8]@(p-HBA)2∙Q[8]@p-HBA as the structural formula.This supramolecular structure was screened for its ability to capture iodine.The experimental results showed that the adsorption efficiency of the supramolecular organic framework material for iodine capture was 43.8%,with an equilibrium adsorption capacity of 223.3 mg/g.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

Bis-naphthalimide-based supramolecular self-assembly system for selective and colorimetric detection of oxalyl chloride and phosgene in solution and gas phase

Two bis-naphthalimide-based supramolecular gelators(NN-3 and NN-4)with a little difference of position of amino groups were designed and synthesized for the detection of oxaloyl chloride and phosgene.Energy transfer could be occurred between two naphthalimide groups in molecules NN-3 and NN-4.Yellow gels NN-3 and NN-4 were formed in some mixed solvents,and nanofibers with different size were obtained in these gels.The self-assembly processes of NN-3 and NN-4 in different solvents were investigated by UV-vis absorption,fluorescent spectra,SEM,FTIR,XRD and NMR.Gelators NN-3 and NN-4 could selectively detect oxaloyl chloride in solution and film states,but detect phosgene only in solution.NN-3exhibited the ratiometric detection ability towards oxaloyl chloride and phosgene with the low limit of detection(LOD)of 210 nmol/L and 90 nmol/L,respectively.NN-4 as the corresponding control sample,it owned the higher LOD towards oxaloyl chloride and phosgene of 12.4μmol/L and 64μmol/L,respectively.Interestingly,films NN-3 and NN-4 could sensitively detect oxaloyl chloride gases with the low LOD of2.0 ppm and 8.34 ppm,respectively.The detection mechanisms of NN-3 and NN-4 were well studied by1H NMR titration,HRMS and theoretical calculation.

Controlling Molecular Packing in Aqueous Metallosupramolecular Self-assembly by Ligand Geometry

The coordination geometry of d8 transition metal complexes has been successfully exploited as a tool to tune photophysical properties and self-assembly pathways of supramolecular polymerization processes,with a focus being primarily placed on organic media.Expanding such controlled supramolecular and photophysical properties to assemblies in aqueous media by molecular design is,however,still challenging due to the difficulty in programming noncovalent interactions in water.Herein,we tackle this challenge by analyzing the aqueous self-assembly of amphiphilic Pt(II)complexes of different molecular geometry in order to control self-assembly and metal−metal interactions in aqueous media.To this end,we have designed two Pt(II)complexes,1 and 2,containing an identical oligophenyleneethynylene(OPE)-based aromatic scaffold that differ in the molecular geometry(linear vs V-shaped)imposed by ligand substitution and studied their comparative self-assembly behavior in aqueous media.Even though both molecules follow the isodesmic mechanism of self-assembly,their structural difference strongly influences the molecular packing in aqueous media,which in turn impacts the photophysical properties(i.e.absence or presence of MMLCT)and the self-assembly outcome.While the molecular geometry for 2 enforces short Pt…Pt contacts driven by an efficient face-to-face stacking of the OPE backbone,the antiparallel packing of 1 with slight translational offset does not allow the formation of short Pt…Pt contacts.Such a distinct interplay of interactions for 1 and 2 in aqueous media leads to significant differences in photoluminescence.

Supramolecular self-assembly of two-component systems comprising aromatic amides/Schiff base and tartaric acid

The gelating properties and thermotropic behaviors of stoichiometric mixtures of aromatic amides 1,2,and the aromatic Schiffbase 3 with tartaric acid(TA)were investigated.Among the three gelators,2-TA exhibited superior gelating ability.Mixture 2-TA exhibits a smectic B phase and an unidentified smectic mesophase during both heating and cooling runs.The results of Fourier transform infrared spectroscopy and X-ray diffraction revealed the existence of hydrogen bonding and rc-ninteractions in 2-TA systems,which are likely to be the dominant driving forces for the supramolecular selfassembly.Additionally,it was established that all of the studied gel self-assemblies and mesophases possess alamellar structure.The anion response ability of the tetrahydrofuran gel of 2-TA was evaluated and it was found that it was responsive to the stimuli of F,Cl,Br,I,AcO.

Bio-inspired supramolecular self-assembly towards soft nanomaterials

Supramolecular self-assembly has proven to be a reliable approach towards versatile nanomaterials based on multiple weak intermolecular forces. In this review, the development of bio-inspired supramolecular self-assembly into soft materials and their applications are summarized. Molecular systems used in bio-inspired ＂bottom- up self-assembly＂ involve small organic molecules, peptides or proteins, nucleic acids, and viruses. Self-assembled soft nanomaterials have been exploited in various applications such as inorganic nanomaterial synthesis, drug or gene delivery, tissue engineering, and so on.

Supramolecular Self-assembly Behaviors of Asymmetric Diblock Copolymer Blends with Hydrogen Bonding Interactions between Shorter Blocks Modelled by Yukawa Potentials

We employed the extended self-consistent field theory to investigate the supramolecular self-assembly behaviors of asymmetric diblock copolymer blends(AB/B’C)with hydrogen bonding interactions between shorter B and B’blocks.The hydrogen bonding interactions are described by Yukawa potentials,where the hydrogen bonding donors and acceptors were modelled as two blocks smeared with opposite screened charges.The hierarchical microstructures with parallelly packed lamellae-in-lamellae(Lam)and 4.8.8 Archimedean tilting pattern(4.8.8)were observed at lower and higher hydrogen bonding density(θ),respectively.The hierarchy of Lam and 4.8.8 were demonstrated by the one-and two-dimensional density profiles and the underlying order of the large-length-scale and small-length-scale microstructures were also clarified.It was found that the 4.8.8 is favorable to the stronger hydrogen bonding density or interactions.Asθincreases,the microphase transition from Lam to 4.8.8 occurs atθ=0.34,which is mainly attributed to the optimization of the electrostatic energy and conformational entropy with sacrificing the interfacial energy.This work can provide a new strategy to understand the supramolecular self-assembly as well as the mechanism behind the formation of complex hierarchical microstructures.

Supramolecular self-assembly and controllable drug release of thermosensitive hyperbranched multiarm copolymers

A novel temperature-responsive hyperbranched multiarm copolymer with a hydrophobic hyperbranched poly(3-ethyl-3-(hydroxymethyl)oxetane)(HBPO) core and thermosensitive poly(N-isopropylacrylamide)(PNIPAM) arms was synthesized via the atom transfer radical polymerization(ATRP) of NIPAM monomers from a hyperbranched HBPO macroinitiator.It was found that HBPO-star-PNIPAM self-assembled into multimolecular micelles(around 60 nm) in water at room temperature according to pyrene probe fluorescence spectrometry,1H NMR,TEM,and DLS measurements.The micelle solution showed a reversible thermosensitive phase transition at a lower critical solution temperature(LCST)(around 32°C) observed by variable temperature optical absorbance measurements.Variable temperature NMR and DLS analyses demonstrated that the LCST transition originated from the secondary aggregation of the micelles driven by increasing hydrophobic interaction due to the dehydration of PNIPAM shells upon heating.The drug loading and release properties of HBPO-star-PNIPAM micelles were also investigated using prednisone acetate as a model drug.The micelles showed a much improved drug encapsulation efficiency and temperature-dependent sustainable release behavior due to the special micellar structure.The micelles exhibited no apparent cytotoxicity against human HeLa cells.

Combination therapy to overcome ferroptosis resistance by biomimetic self-assembly nano-prodrug

Ferroptosis has emerged as a potent form of no-apoptotic cell death that offers a promising alternative to avoid the chemoresistance of apoptotic pathways and serves as a vulnerability of cancer.Herein,we have constructed a biomimetic self-assembly nano-prodrug system that enables the co-delivery of gefitinib(Gefi),ferrocene(Fc)and dihydroartemisinin(DHA)for the combined therapy of both ferroptosis and apoptosis.In the tumor microenvironment,this nano-prodrug is able to disassemble and trigger drug release under high levels of GSH.Interestingly,the released DHA can downregulate GPX4 level for the enhancement of intracellular ferroptosis from Fc,further executing tumor cell death with concomitant chemotherapy by Gefi.More importantly,this nano-prodrug provides highly homologous targeting ability by coating related cell membranes and exhibits outstanding inhibition of tumor growth and metastasis,as well as no noticeable side-effects during treatments.This simple small molecular self-assembled nano-prodrug provides a new reasonably designed modality for ferroptosis-combined chemotherapy.

Efficient conversion of lignin waste and self-assembly synthesis of C@MnCo_(2)O_(4)for asymmetric supercapacitors with high energy density

Lignin waste from the papermaking and biorefineries industry is a significantly promising renewable resource to prepare advanced carbon materials for diverse applications,such as the electrodes of supercapacitors;however,the improvement of their energy density remains a challenge.Here,we design a green and universal approach to prepare the composite electrode material,which is composed of lignin-phenolformaldehyde resins derived hierarchical porous carbon(LR-HPC)as conductive skeletons and the self-assembly manganese cobaltite(MnCo_(2)O_(4))nanocrystals as active sites.The synthesized C@MnCo_(2)O_(4)composite has an abundant porous structure and superior electronic conductivity,allowing for more charge/electron mass transfer channels and active sites for the redox reactions.The composite shows excellent electrochemical performance,such as the maximum specific capacitance of~726 mF cm^(-2)at 0.5 mV s^(-1),due to the significantly enhanced interactive interface between LR-HPC and MnCo_(2)O_(4)crystals.The assembled all-solid-state asymmetric supercapacitor,with the LR-HPC and C@MnCo_(2)O_(4)as cathode and anode,respectively,exhibits the highest volumetric energy density of 0.68 mWh cm^(-3)at a power density of 8.2 mW cm^(-3).Moreover,this device shows a high capacity retention ratio of~87.6%at 5 mA cm^(-2)after 5000 cycles.

Analysis on the formation principle and present situation of nano phase state of multi-component self-assembly of traditional Chinese compound medicine decoction

Traditional Chinese medicine decoction is a complex polydispersed phase system containing real solution,colloid solution,emulsion and suspension.The compound decoction of traditional Chinese medicine has complex components,including saponins,alkaloids,polysaccharides,flavonoids,amino acids and so on,which can be self-assembled to form gels,fibers,micelles,vesicles and so on.The self-assembled nano-phase not only neutralizes the single drug and reduces the toxicity and side effects,but also has its own pharmacological effects,which complement each other to achieve synergistic effect,so as to achieve the role of drug supplement,which is of research significance.The formation principle,solubilization and synergism principle and characterization method of multi-component self-assembly of traditional Chinese medicine compound decoction are discussed in this paper.

Nano/Micro-Structural Supramolecular Biopolymers: Innovative Networks with the Boundless Potential in Sustainable Agriculture

Sustainable agriculture plays a crucial role in meeting the growing global demand for food while minimizing adverse environmental impacts from the overuse of synthetic pesticides and conventional fertilizers.In this context,renewable biopolymers being more sustainable offer a viable solution to improve agricultural sustainability and production.Nano/micro-structural supramolecular biopolymers are among these innovative biopolymers that are much sought after for their unique features.These biomaterials have complex hierarchical structures,great stability,adjustable mechanical strength,stimuli-responsiveness,and self-healing attributes.Functional molecules may be added to their flexible structure,for enabling novel agricultural uses.This overview scrutinizes how nano/micro-structural supramolecular biopolymers may radically alter farming practices and solve lingering problems in agricultural sector namely improve agricultural production,soil health,and resource efficiency.Controlled bioactive ingredient released from biopolymers allows the tailored administration of agrochemicals,bioactive agents,and biostimulators as they enhance nutrient absorption,moisture retention,and root growth.Nano/micro-structural supramolecular biopolymers may protect crops by appending antimicrobials and biosensing entities while their eco-friendliness supports sustainable agriculture.Despite their potential,further studies are warranted to understand and optimize their usage in agricultural domain.This effort seeks to bridge the knowledge gap by investigating their applications,challenges,and future prospects in the agricultural sector.Through experimental investigations and theoretical modeling,this overview aims to provide valuable insights into the practical implementation and optimization of supramolecular biopolymers in sustainable agriculture,ultimately contributing to the development of innovative and eco-friendly solutions to enhance agricultural productivity while minimizing environmental impact.

Sensitive and Selective Fluorescent and Colorimetric Sensor for Ag^＋ Based on the Supramolecular Self-Assembly in Semi-Water

在用超级快方法的半水的离子的 ultratrace 层次的特定的识别仍然是为环境监视的挑战。此处，我们报导一荧光灯并且 colormetric 传感器(ZH ) 基于超分子自己组装，其结构被银离子的 ultratrace 的增加破坏。这个过程支持了可见颜色改变的肉眼或与一个宽 pH 范围一起熄灭的荧光紧张。系统的研究揭示了很高的选择(0.

Synthesis and Crystal Structure of a New Noble Metalcontaining Supramolecular Self-assembly with Decamethylcucurbit[5]uril

A new supramolecular self-assembly [Li(H2 O)2]2[(H2 O@Me10 CB[5])][PtC l6]·7 H2 O(1, Me10 CB[5] = decamethylcucurbit[5]uril), has been successfully constructed with Me10 CB[5] and [PtCl6]^(2-) anion in the presence of lithium cation(Li+). Single-crystal X-ray diffraction study reveals that compound 1 crystallizes in monoclinic space group P21/n with a = 11.1681(18), b = 28.5425(4), c = 18.9342(3) ?, β = 99.0143(15)°, V = 5961.02(16) ?~3, Z = 4, F(000) = 3224, μ = 2.714 mm^(-1), R = 0.0470 and wR = 0.1076(I > 2σ(I)). In the supramolecular self-assembly, two of the portal carbonyl oxygen atoms of Me10 CB[5] are coordinated to Li+ cation, yielding a "half-open" molecular capsule. Then adjacent molecular capsules are connected with each other through hydrogen-bonding to form a one-dimensional(1 D) supramolecular chain structure. The [PtCl6]^(2-) anions are fixed on one side of the 1 D supramolecular chain through supramolecular interactions. The thermal stability, electronic valence and morphology of compound 1 are also investigated.