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.

Synthesis of a New Porphyrin-fluorescein Hybrid and its Supramolecular Self-assembly with Amino-porphyrinatomanganese(Ⅲ) by Hydrogen-bonding

A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomanganese [Mn (p-APTPP)Cl] by hydrogen-bonding was studied using fluorescence spectroscopic titration and ESI-MS.

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.

Chiral liquid crystals based on pillararene and supramolecular self-assembly-induced chirality amplification

Macrocyclic liquid crystals combine the unique property of liquid crystals and excellent supramolecular assembly ability of macrocyclic compounds.It is a significant challenge to make rational use of the advantages of macrocyclic compounds to prepare new macrocyclic mesogens.Pillararenes,a type of macrocycles with rigid pillar-shaped frameworks and easy-tofunctionalize property,are excellent building blocks to fabricate liquid crystal materials.However,the site-selective modification property of pillararene has been rarely exploited to tailor liquid crystal behaviors.Previously reported pillararene-based liquid crystal systems are almost prepared by per-functionalized pillararenes.Herein,we report the regulation of chiral liquid crystal behaviors by different derivatization of pillararene.Lyotropic and thermotropic liquid crystals with different chirality were obtained by self-assembly of pillararene with different numbers of cholesterol groups.The bridge between thermotropic liquid crystal and lyotropic liquid crystal based on pillararene is built.In addition,the chirality of the mesogens can be amplified through supramolecular self-assembly driven by noncovalent interactions.Based on the different liquid crystal behaviors,the optical signal of the pillararene-based chiral liquid crystals was used to fabricate an information encryption system.This work provides a simple strategy to regulate liquid crystal behaviors via pillararene-based mesogens and realizes information encryption through the combination of different types of liquid crystals.

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.

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

Specific recognition of ultratrace levels of ions in semi-water using super-quicker methods is still a challenge for environmental monitoring. Herein we report a fluorescent and colormetric sensor （ZH） based on supramolecular self-assembly, whose structure was destroyed by the addition of ultratrace of silver ions. The process promoted either naked eye visible color changes or fluorescence intensity quenched in conjunction with a wide pH range. Systematic studies revealed very high selectivity （0.07 μmol/L） for silver ions, and other common cations, e.g., Hg^2＋, Cu^2＋, Cd^2＋, Pb^2＋ had nearly no influence on the sensing behavior. This sensor also served as a multiple use of component in sensing materials by addition of I^- into the mixture of ZH and Ag^＋ （about 5 times）. What＇s more, ZH containing filter paper emerged distinct color and fluorescence changes upon exposure to silver （Ag^＋）, which could be used as a portable method to undertake field testing for Ag^＋.

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.

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.

Supramolecular self-assembly for delivery of oligonucleotides and its phototriggered unpacking in living cells

Two photolabile amphiphilic supramolecules were designed and synthesized with mono-dendrite and tri-dendrite, which can reversibly self-assemble to spheroid and wedge-shaped nanoparticles. With multiple branches of terminal amine labeled PEG, these nanoparticles can associate with a negatively charged oligonucleotide and their usage for oligonucleotide delivery was evaluated. Oligonucleotide/nanoparticle complex containing tri-dendrite can efficiently deliver oligonucleotide into cells via endocytosis, while the complex containing mono-dendrite almost lost their ability to deliver oligonucleotide. Further light activation triggered the dissociation of tri-dendrite supramolecular assembly via 1,4- and 1,6-quinone-methide rearrangement, leading to the efficient unpacking of the oligonucleotide in cells.

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.

Hollow tubes constructed by carbon nanotubes self-assembly for CO_(2) capture

Carbon nanotubes(CNTs)have garnered significant attention in the fields of science,engineering,and medicine due to their numerous advantages.The initial step towards harnessing the potential of CNTs involves their macroscopic assembly.The present study employed a gentle and direct self-assembly technique,wherein controlled growth of CNT sheaths occurred on the metal wire’s surface,followed by etching of the remaining metal to obtain the hollow tubes composed of CNTs.By controlling the growth time and temperature,it is possible to alter the thickness of the CNTs sheath.After immersing in a solution containing 1 g/L of CNTs at 60℃ for 24 h,the resulting CNTs layer achieved a thickness of up to 60μm.These hollow CNTs tubes with varying inner diameters were prepared through surface reinforcement using polymers and sacrificing metal wires,thereby exhibiting exceptional attributes such as robustness,flexibility,air tightness,and high adsorption capacity that effectively capture CO_(2) from the gas mixture.

A Non-parametric Gradient-Based Shape Optimization Approach for Solving Inverse Problems in Directed Self-Assemblyof Block Copolymers

We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).

Morphological Evolution of Self-Assembled Sodium Dodecyl Sulfate/Dodecyltrimethylammonium Bromide@Epoxy-β-Cyclodextrin Supramolecular Aggregates Induced by Temperature

Bio-based cyclodextrins(CDs)are a common research object in supramolecular chemistry.The special cavity structure of CDs can form supramolecular self-assemblies such as vesicles and microcrystals through weak interaction with guest molecules.The different forms of supramolecular self-assemblies can be transformed into each other under certain conditions.The regulation of supramolecular self-assembly is not only helpful to understand the self-assembly principle,but also beneficial to its application.In the present study,the self-assembly behavior of epoxy-β-cyclodextrin(EP-β-CD)and mixed anionic and cationic surfactant system(sodium dodecyl sulfate/dodecyltrimethylammonium bromide,SDS/DTAB)in aqueous solution was studied.Morphological and particle size characterization found that the SDS/DTAB@EP-β-CD complex,as the basic building unit,self-assembled into worm-like micelles at lower temperatures and vesicles at higher temperatures.Nuclear magnetic resonance(NMR)and Fourier transform infrared spectroscopy(FT-IR)analysis revealed that the driving force for the formation of vesicles and worm-like micelles was the hydrogen bonds between EP-β-CD molecules,while water molecules played an important role in promoting vesicle formation between SDS/DTAB@EP-β-CD units.Herein,the mechanism of the morphologic transformation of SDS/DTAB@EP-β-CD supramolecular aggregates induced by temperature was elucidated by exploring the self-assembly process,which may provide an excellent basis for the development of delivery carriers.

Confined cobalt single-atom catalysts with strong electronic metal-support interactions based on a biomimetic self-assembly strategy

Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η10 at 288 mV;Tafel slope of 44 mV dec-1),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

Layer by Layer Self-assembly Fiber-based Flexible Electrochemical Transistor

Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.

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.