Architecture Design and Interface Engineering of Self-assembly VS_(4)/rGO Heterostructures for Ultrathin Absorbent

The employment of microwave absorbents is highly desirable to address the increasing threats of electromagnetic pollution.Importantly,developing ultrathin absorbent is acknowledged as a linchpin in the design of lightweight and flexible electronic devices,but there are remaining unprecedented challenges.Herein,the self-assembly VS_(4)/rGO heterostructure is constructed to be engineered as ultrathin microwave absorbent through the strategies of architecture design and interface engineering.The microarchitecture and heterointerface of VS_(4)/rGO heterostructure can be regulated by the generation of VS_(4) nanorods anchored on rGO,which can effectively modulate the impedance matching and attenuation constant.The maximum reflection loss of 2VS_(4)/rGO40 heterostructure can reach−43.5 dB at 14 GHz with the impedance matching and attenuation constant approaching 0.98 and 187,respectively.The effective absorption bandwidth of 4.8 GHz can be achieved with an ultrathin thickness of 1.4 mm.The far-reaching comprehension of the heterointerface on microwave absorption performance is explicitly unveiled by experimental results and theoretical calculations.Microarchitecture and heterointerface synergistically inspire multi-dimensional advantages to enhance dipole polarization,interfacial polarization,and multiple reflections and scatterings of microwaves.Overall,the strategies of architecture design and interface engineering pave the way for achieving ultrathin and enhanced microwave absorption materials.

Effects of Doubled_CO_2 Concentration on Ultrastructure, Supramolecular Architecture and Spectral Characteristics of Chloroplasts from Wheat

Wheat ( Triticum aestivum L.) plants were grown under ambient and doubled_CO 2(plus 350 μL/L) concentration in cylindrical open_top chamber to examine their effects on the ultrastructure, supramolecular architecture, absorption spectrum and low temperature (77 K) fluorescence emission spectrum of the chloroplasts from wheat leaves. The results were briefly summarized as follows: (1) The wheat leaves possessed normally developed chloroplasts with intact grana and stroma thylakoid membranes; The grana intertwined with stroma thylakoid membranes and increased slightly in stacking degree and the width of granum, in spite of more accumulated starch grains within the chloroplasts than those in control; (2) The particle density in the stacked region of the endoplasmic fracture face (EFs) and protoplasmic fracture face (PFs) and in the unstacked region the endoplasmic fracture face (EFu) and the protoplasmic fracture face (PFu) was significantly higher than that of control. Furthermore, in some cases many more particles on EFs faces of thylakoid membranes appeared as a paracrystalline particle array; (3) The variations in the structure of chloroplasts were consistent with the absorption spectra and the low temperature (77 K) fluorescence emission spectra of the chloroplasts developed under the doubled_CO 2 concentration. Results indicate that the capability of light energy absorption of chloroplasts and regulative capability of excitation energy distribution between PSⅡ and PSⅠ were raised by doubled_CO 2 concentration. This is very favorable for final productivity of wheat.

Synthesis,Crystal Structure and Water Vapor Adsorption Property of a New Supramolecular Architecture

A new complex, [Cu（HL）（phen）（H2O）]·4H2O（1, H3L·HCl = 5-（（4-carboxypiperidin-1-yl）methyl）isophthalic acid hydrochloride, phen = 1,10-phenanthroline）, has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.5520（14）, b = 12.6659（12）, c = 15.5006（14） A, β = 97.224（2）o, V = 2834.3（5） A3, Z = 4, C27H33N3O11 Cu, Mr = 639.10, Dc = 1.498 g/cm3, μ = 0.837 mm-1, S = 1.047, F（000） = 1332, the final R = 0.0423 and w R = 0.1118 for 18772 observed reflections（I 〉 2σ（I））. The compound is a Cu（Ⅱ） centre mononuclear molecule in the asymmetric unit. The independent binuclear [Cu2（HL）2（phen）2] units are bridged to form a three-dimensional（3D） supramolecular polymer by extensive hydrogen bonds and π-π non-covalent bonding interactions. Moreover, thermogravimetric（TG） analysis and gas adsorption property of 1 were also discussed.

A Novel Borophosphate Coordination Polymer with Sandwich-type Supramolecular Architecture

A novel borophosphate (Hmel)3{Co2[(mel)2(HPO4)2(PO4)]·H3BO3·H2O} (mel= melamine) has been synthesized under mild solvothermal conditions. The structure of the compound exists a high ordered organic-inorganic sandwich-type supramolecular architecture via metal-coordination, hydrogen bonds and π-π stacking interactions.

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.

Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers

Molecular weaving is a powerful approach to make molecularly woven materials that have showed unprecedented characteristics and properties intrinsically distinct to those of non-woven materials.We here report a facile and efficient approach for the synthesis of 2D woven supramolecular polymers by differentiated self-assembly through orthogonal noncovalent interactions.Importantly,the difference in binding strength of two orthogonal noncovalent interactions can be used to control the process of molecular weaving.Consequently,single-layered 2D woven supramolecular polymers were synthesized and fully characterized by various techniques.This study demonstrates a controllable method for molecular weaving,and will significantly hasten the development of molecularly woven materials.

Two Zinc Architectures:A Mononuclear Complex and a 2D Wave-like Organic-inorganic Hybrid Layer

Self-assembly of Zn（NO3）2·6H2O and 2,3,5,6-tetrabromoterephthalic acid（H2TBTA） gave rise to two new zinc metal-organic frameworks,Zn（HTBTA）2（phen）2·H2O（1） and Zn（TBTA）1/2（μ2-OH）（H2O）·0.25EtOH（2）.Complex 1 is a mononuclear molecule.The hydrogen bonding interactions further connect the mononuclear molecules to generate a 2D supramolecular architecture.Complex 2 is a 2D organic-inorganic hybrid layer framework constructed from 1D rod-shaped secondary building units.

Preparing three-dimensional graphene architectures: Review of recent developments

The recent development of synthesis processes to assemble graphene sheets into porous three-dimensional （3D）macroscopic structures are reviewed, including our efforts on 3D graphene structures. Mechanisms for building 3D graphene architectures and their composite materials are also summarized. The functional systems based on 3D graphene architectures provide a significant enhancement in the efficacy due to their unique structures and properties.

Mechanism of N-octadecyl-N′-maleoyl-L-phenylalanine self-assembled into supramolecular structures

N-Octadecyl-N1-maleoyl-L-phenylalanine （ODMA-L-Phe） was synthesized through the condensation, deprotection and acid- ylation reaction of BOC-L-phenylalanine, octadecylamine and maleic anhydride. ODMA-L-Phe can self-assemble in some organic solvents and turned them into thermally reversible physical supramolecular organogels. The morphology of ODMA-L-Phe aggregates was characterized by polarized optical microscopy （POM） and field emission scanning electron microscope （FE-SEM）. The aggregates of ODMA-L-Phe were needle-like fibrils with diameters of approximately 100-200 nm. The mechanism of ODMA- L-Phe self-assembly in organic solvents was investigated using XH NMR and circular dichroism （CD）. The results indicated that hydrogen bonding was one of the main driving forces for the self-assembly of ODMA-L-Phe.

Recent advances in two-step energy transfer light-harvesting systems driven by non-covalent self-assembly

Sequential energy transfer is ubiquitous in natural light-harvesting systems(LHSs),which greatly promotes the exploitation of light energy.The LHSs in nature are sophisticated supramolecular assemblies of chlorophyll molecules that carry out efficient light harvesting through cascade energy transfer process.Inspired by nature,scientists have paid much attention to fabricate stepwise LHSs based on assorted supramolecular scaffolds in recent years.Light-harvesting antennas and energy acceptors can be accommodated in particular scaffolds,which offer great convenience for energy transfer between them.These systems not only further mimic photosynthesis,but also demonstrate many potential applications,such as photocatalysis,tunable luminescence,and information encryption,etc.In this review article,aiming at offering a practical guide to this emerging research field,the introduction of construction strategies towards sequential LHSs will be presented.Different scaffolds are classified and highlighted,including host-guest assemblies,metal-coordination assemblies,as well as bio-macromolecular and other supramolecular scaffolds.

Tunable aggregation-induced fluorescent and pressure-responsive luminescence supramolecular cages achieved by subcomponent self-assembly

Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-vinylene)(u-COPV)suspended by the truxene skeleton,the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission(AIE)accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation.In particular,the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.

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.

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.

A Two-dimensional Supramolecular Complex Constructed by 1,10-Phenanthroline Derivative Ligand:Synthesis,Structure and Luminescence

An unusual two-dimensional supramolecular complex, namely, [Cd2（Cl）4（L）2]（1）, has been synthesized by 2-（1 H-imidazo[4,5-f][1,10]phenanthrolin-2-yl）phenol（L） and CdCl2·2.5H2O under hydrothermal conditions. The compound was characterized by elemental analysis, TG and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.151（2）, b = 14.119（3）, c = 14.744（3） ？, α = 115.744（4）, β = 108.063（4）, γ = 93.371（4）o, V = 1762.7（7） A°^3, Z = 2, C（38）H（24）Cd2Cl4N8O2, Mr = 991.25, Dc = 1.868 g/cm^3, F（000） = 976, μ（Mo Ka） = 1.560 mm^-1, R = 0.0639 and w R = 0.1307. In 1, two Cd（II） atoms are bridged by two chroline atoms to give a dimer. Neighboring dimers are linked by N–H···Cl hydrogen bonds to afford supramolecular chains, which are further joined together by π-π interactions to result in a supramolecular layer. In addition, luminescent property and thermal behavior of compound 1 have been studied.

Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

A new supramolecular compound （4,4＇-bipyH）4[SiW12O40]（4,4＇-bipy） （4,4＇-bipy = 4,4＇-bipyridine） was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767（12）, b = 21.1879（11）, c = 15.6942（8） A, β = 97.068（3）°, V = 7351.3（7） A3, Cs0H44N10040SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F（000） = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiWl2O40]4- anion, one 4,4＇-bipy and four protonated （4,4＇-bipyH）＋ cations. The [SiWl2O40]4- anion and protonated 4,4＇-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.

Supramolecular Sheet Co(Ⅱ) Complex Assembled by Hydrogen Bond

The title complex, [ [ Co （Py） 2 （H20） 2 （ NO3 ）2 ] ] n （ 1 ） was synthesized by liquid/liquid diffusion method at room temperature. The complex crystallizes in monoclinic, space group P2 （1）/C, with a = 0.8775（6）nm, b=1.171 5（8）nm, c=0.7518（5）nm, V=0.739 3（9）nm3, C10H14CoN4O8, Mr= 377.18, Dc=1.694g/cm^3, μ=1.210mm^-1, F（000）=386, Z=2, the final R=0.0229 and wR= 0.066 1 for 3 137 observed reflections （I〉2σ（I））. In the structure of 1, the center atom of cobalt revealed a centrosymmetric, six-coordinate structure, with two Py ligands, two monodentate nitrate groups and two water molecules. It is notable that a series of hydrogen bonds （O-H…O） formed two kinds of rings exist in the structure, which linked neighboring six-coordinate polymer into a two-dimensional H-bonding network, and then assembled into a three-dimensional supramolecular architecture through electrostatic and hydrophobic interaction. In the structure, supramolecular sheet was observed, which contains alte .rnative organic and inorganic layers.

Study on the α-cyclodextrin/poly(ethylene glycol) self-assembly supramolecular nanoparticles for drug delivery

This paper reports the synthesis and drug delivery properties of a novel supramolecular nanoparticle.α-Cyclodextrins(α-CD) were threaded on cinnamic acid modified poly(ethylene glycol) to form inclusion complex nanoparticles by supramolecular self-assemble.The anti-tumor drug doxorubicin was loaded in the nanoparticles and released in vitro to study the drug release behavior and the anti-tumor effects.The structure and morphology of the nanoparticles were characterized by nuclear magnetic resonance,X-ray diffraction,ultraviolet absorbance,dynamic laser scattering,scanning electronic microscopy,transmission electron microscopy and atom force microscopy.The distribution of the drug loaded nanoparticles in cells and the anti-tumor effects were studied by confocal laser microscopy.The results demonstrate that the supramolecular nanoparticle is biocompatible and it is a promising carrier for drug delivery systems.

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.