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.

Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy

Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing technologies.This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques.The solution of tetrakis(4-sulfonatophenyl)porphyrin(TPPS)was induced by chiral amino acids(L/D-arginine and L/D-serine)to selfassemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate(SDS).The structures show precise line widths(5.5μm)and gaps(18μm).Using in situ optical microscopy and second harmonic generation(SHG)microscopy,the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated.It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies.This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.

Self-assembly of porphyrins on perovskite film for blade-coating stable large-area methylammonium-free solar cells

Phase transition and phase separation of formamidinium-cesium(FA-Cs)perovskite during the fabrication and operation processes reduce the efficiency and stability of perovskite solar cells(PSCs).Here,we develop an in situ molecular self-assembly approach on perovskite surface using an amine nickel porphyrin(NiP).The NiP doped perovskite precursor solution was deposited on substrate by blade-coating under ambient condition.NiP molecules self-assemble into supramolecule bound on perovskite surface during the vacuum-assisted process.Such a modification controls the perovskite grain growth to generate the uniform perovskite film.The supramolecule can release the residual lattice strain to inhibit the phase transition of perovskite film,and promote the charge extraction and transport to suppress the phase separation of FA-Cs perovskite during long-term illumination condition.Consequently,the best efficiency of large-area NiP-based FA-Cs-PSCs with the active area of 1.0 cm2 is up to 20.3%(certified as 19.2%),which is close to the record efficiency(20.37%)by blade-coating.Unencapsulated NiP-doped device reveals the remarkably improved overall stabilities.This work affords a novel way to address the phase transition and phase separation in FA-Cs perovskite.

Synthesis of a Benzenethiol-derivatized Porphyrin for Self-assembly

The synthesis of a benzenethiol-derivatized porphyrin for flat-lying self-assembly on gold substrates is described. Acetyl protected thiol is not stable enough in Pd-catalyzed reactions. While acrylate derivatives protected thiol group shows good tolerance in Pd-catalyzed borylations and Suzuki-Miyaura coupling reactions and no catalyst poisoning was observed.

Tunneling Electron Induced Fluorescence from Single Porphyrin Molecules Decoupled by Striped-Phase Octanethiol Self-assembled Monolayer

We investigate tunneling electron induced luminescence from isolated single porphyrin molecules that are decoupled by striped-phase self-assembled monolayer of octanethiol from the underneath Au（111） substrate. Intrinsic single-molecule electroluminescence has been realized by such decoupling at both bias polarities. The photon emission intensity acquired from the molecular lobe is found stronger than that from the molecular center. These re- sults provide useful information on the understanding of electroluminescent behavior and mechanism in molecular tunnel junctions.

Target-triggered hairpin-free chain-branching growth of DNA dendrimers for contrast-enhanced imaging in living cells by avoiding signal dispersion

The development of amplification strategies is one of the central challenges for detection of lowabundance targets. One-to-many(1:M) amplification strategies in which one target lights many signal probes, has improved the detection sensitivity in bulk solution, but with discounted contrast in cell imaging, because the lighted probes are dissociative and dispersible. In this work, a one-to-large(1:L) signaling mechanism, in which the lighted probes were orderly connected to each other, was conceptually proposed to enhance the contrast in cell imaging by avoiding signal dispersion in amplification. Accordingly,target-triggered hairpin-free chain-branching assembly(HFCBA) holds great potential to implement the1:L mechanism, but using it in cell imaging has yet to be demonstrated. As a proof of concept, a group of probes were first programmed to implement mi RNA-21-triggered HFCBA. After transfection of probes,gradually-growing signal flares in cells were monitored along with the growth of DNA dendrimers;and the in situ fluorescence accumulation in HFCBA resulted in highly-enhanced contrast to the surrounding by avoiding signal dispersion in amplification. The contrast-enhanced imaging with signal amplification is significant for biological analysis and molecular medicine. We expect the 1:L mechanism will provide a new thought for high-performance imaging of biomarkers in cells.

An ionizable supramolecular dendrimer nanosystem for effective siRNA delivery with a favorable safety profile

Gene therapy using small interfering RNA(siRNA)is emerging as a novel therapeutic approach to treat various diseases.However,safe and efficient siRNA delivery still constitutes the major obstacle for clinical implementation of siRNA therapeutics.Here we report an ionizable supramolecular dendrimer vector,formed via self-assembly of a small amphiphilic dendrimer,as an effective siRNA delivery system with a favorable safety profile.By virtue of the ionizable tertiary amine terminals,the supramolecular dendrimer has a low positively charged surface potential and no notable cytotoxicity at physiological pH.Nonetheless,this ionizable feature imparted sufficient surface charge to the supramolecular dendrimer to enable formation of a stable complex with siRNA via electrostatic interactions.The resulting siRNA/dendrimer delivery system had a surface charge that was neither neutral,thus avoiding aggregation,nor too high,thus avoiding cytotoxicity,but was sufficient for favorable cellular uptake and endosomal release of the siRNA.When tested in different cancer cell lines and patient-derived cancer organoids,this dendrimer-mediated siRNA delivery system effectively silenced the oncogenes Myc and Akt2 with a potent antiproliferative effect,outperforming the gold standard vector,Lipofectamine 2000.Therefore,this ionizable supramolecular dendrimer represents a promising vector for siRNA delivery.The concept of supramolecular dendrimer nanovectors via self-assembly is new,yet easy to implement in practice,offering a new perspective for supramolecular chemistry in biomedical applications.

Chiral porphyrin assemblies

Porphyrins are among the most important macrocycles because they perform many essential functions in living systems and serve as building blocks in many functional materials.Incorporating the chirality into porphyrins can aid biomimetic research and the exploration of new functional materials.In this review,recent developments in chiral porphyrin assemblies are highlighted.The review is mainly divided into two sections:the different strategies for constructing chiral porphyrin assemblies and the applications.The formation of chiral porphyrin assemblies can be from porphyrin molecules substituted with chiral groups;achiral porphyrins induced by chiral additives and spontaneous deracemizations of achiral porphyrins during the assemblies.We also provide an overview of the applications of chiral porphyrin assemblies in chiral sensing,asymmetry catalysis,circularly polarized luminescence,and so on.The further challenge in the field is discussed.

Characterization of self-assembled monolayers of porphyrins bearing multiple-thiol and photoelectric response

Self-assembled monolayers（SAMs） of thiol-derivatized porphyrin molecules on Au substrate have attracted extensively interest for use in sensing,optoelectronic devices and molecular electronics.In this paper,tetra-[p-（3-mercaptopropyloxy）-phenyl]porphyrin was synthesized and self-assembled with thiol on Au substrate for porphyrin SAMs（PPS 4）.The electrochemical results demonstrated that PPS 4 could form excellent SAMs on gold surface.Self-assembled nanojunctions of PPS 4 were fabricated by using gold nanogap electrodes（gap width：ca.100 nm）.With the light on/off,the nanojunctions showed current high/low as nanometer scaled photo switch.

Morphology-controlled porphyrin nanocrystals with enhanced photocatalytic hydrogen production

Molecular self-assembly is a natured-inspired strategy to integrate individual functional molecules into supramolecular nanostructured materials through noncovalent bond interactions for solar to fuel conversion.However,the design and engineering of the morphology,size,and orderly stacking of supramolecular nanostructures remain a great challenge.In this study,regular porphyrin nanocrystals with different orderly stacked structures are synthesized through noncovalent self-assembly of Pt(II)meso-tetra(4-carboxyphenyl)porphine(PtTCPP),using surfactants with different electronegativity.The synergy of noncovalent bond interactions between porphyrin molecules,and between porphyrin molecules and surfactants resulted in different molecular packing patterns.Due to the spatial ordering of PtTCPP molecules,the different nanocrystals exhibit both collective optical properties and morphology-dependent activities in photocatalytic hydrogen production.The measurements of the photodeposition of dual cocatalysts showed that the photogenerated electrons and holes selectively aggregated at different active sites,revealing separation pathways and directional transfer of photogenerated electrons and holes in the assemblies.This study provides a new strategy to exert rational control over porphyrin self-assembly nanocrystals for highly efficient water splitting.

Nonlinear Optical Properties of Porphyrin Derivatives with Electron-donating or Electron-withdrawing Substituents

To investigate photoelectric properties of meso-extended porphyrin derivatives with electron-donating or elec- tron-withdrawing substituents, a series of functionalized porphyrin materials have been designed and synthesized by Suzuki coupling reaction. The meso-extended structures were fully characterized by IH NMR, IR spectroscopy and mass spectrometry. The photophysical properties of porphyrin derivatives were carefully examined by UV-Visible and fluorescence spectra, and the solvatochromic effect was observed and discussed. In particular, Z-scan technique was employed to characterize the third-order nonlinear optical （NLO） properties of the products such as nonlinear absorption and refraction, the third-order nonlinear refractive indexes （x（3）-value） of these porphyrin derivatives achieved 3.9 × 10-12 esu. In addition, the compounds could be self-assembled into highly organized morphologies through phase-exchange method. All the results indicated that the discotic materials have the potential for optoelec- tronic applications.

基于静电吸引的自组装树状超分子复合物

A new kind of dendritic supramolecular complex with porphyrin as a core-centre was prepared based on electrostatic attraction between tetraphenylporphyrinsulfonate anlon and polyether dendritic cations, which was confirmed by 1 H NMR, IR and elementary analysis.

Highly ordered arrangement of meso-tetrakis(4-aminophenyl)porphyrin in self-assembled nanoaggregates via hydrogen bonding

meso-Tetrakis（4-aminophenyl）porphyrin（TAPP） can self-assemble into nanostructures with different morphologies by a phase-transfer method.The morphologies（nanospheres,nanorods and nanothorns）of porphyrin nanoaggregates could be easily tuned just by changing the concentration of porphyrin in a proper solvent at room temperature.HRTEM images revealed the formation of highly ordered supramolecular arrays of TAPP,i.e. superlattice of TAPP molecules in nanoaggregates,which agreed well with the size of one molecule of TAPP.UV–vis absorption spectra showed an obvious red shift of the Soret band of TAPP,indicating the formation of J-aggregates of TAPP in nanoaggregates.

Nanosize Catalysis Nanoscale Moleculars Structures

The catalytic system is investigated in a computer chromatography. The sorbent represents the nanostructure composite with hardpolymer electrolyt. As the nanostructure polymeric system, it used dendrimer who are absorbed on a surface with formation of monolayer. In chromatography column watch dimensional effect. The size of a particle carries out a role of temperature. In the article, investigate solvatation and dimensional effect reaction self-assembling gas dimmers. Distance critical radius H＋ transfer define equation： rcr = 2rs. Reaction accompaniment transfer energy. Transfer energy realize on exchange-resonanse mechanism.

亲和吸附固体基质室温磷光法测定痕量糖与疾病测报

在外重原子微扰剂LiAc存在下,3.5代树枝状分子-卟啉(3.5G-D-P)分子中3.5代树枝状分子(3.5G-D)与卟啉(P)在聚酰胺膜(PAM)上能发射强而稳定的室温磷光,Tween-80对3.5G-D与P的磷光信号有显著的增敏作用,而且Tween-80-3.5G-D-P标记麦胚凝集素(WGA)的产物(Tween-80-3.5G-D-P-WGA)能与糖(G)发生特异性的亲和吸附(AA)反应,其亲和吸附反应产物保持了3.5G-D与P双发光分子RTP的优良特性,且?Ip值与G的含量呈现线性关系,据此建立了Tween-80-3.5G-D-P双发光分子标记WGA亲和吸附固体基质室温磷光法(AA-SS-RTP)测定痕量G的新方法.本法的检出限为0.13 fg spot-1(1.7×10-12 mol l-1,3.5G-D)和0.14 fg spot-1(2.2×10-12 mol l-1,P).无论用3.5G-D或P的激发/发射波长测定血清中G的含量,结果都与酶联免疫法(ELISA)相吻合.

4.0代树枝状分子-卟啉标记伴刀豆凝集素亲和吸附固体基质室温磷光法测定人血清中甲胎蛋白异质体

提出一种4.0代树枝状分子(4.0G-D)-卟啉(P)双发光分子新的磷光标记试剂(4.0G-D-P).基于4.0G-D-P标记伴刀豆凝集素(Con A)的产物(4.0G-D-P-Con A)能在聚酰胺素膜(PAM)上发射强而稳定的室温磷光(RTP),而且该标记产物能与甲胎蛋白异质体(AFP-V)发生特异性的亲和吸附(AA)反应,其反应产物保持了4.0G-D-P双发光分子RTP的优良特性,且ΔIp值与AFP-V的含量呈线性关系,加入Tween-80可以提高ΔIp值,据此建立了Tween-80-4.0G-D-P双发光分子标记Con A亲和吸附固体基质室温磷光法(AA-SS-RTP)测定人血清中AFP-V的新方法.直接法的检出限为0.31 pg/mL(4.0G-D)和0.43 pg/mL(P),灵敏度较高.无论用4.0G-D或P的激发/发射波长测定人血清中AFP-V的含量,结果与酶联免疫法(ELISA)相吻合.

卟啉树状大分子化合物的合成及其抗活性氧作用

目的研究金属卟啉树状大分子化合物的合成并考察其作为超氧化物歧化酶(SOD)和过氧化氢酶(CAT)双功能模拟酶的活性。方法通过收敛式合成法合成酸性表面二价铜卟啉树状大分子化合物。用核黄素-蛋氨酸光照法进行抗活性氧作用实验。结果与结论合成了5个酸性表面二价铜卟啉化合物。药理数据显示,树状大分子化合物体积的大小将会影响其抗活性氧能力。

Self-Assembled Materials for Catalysis

The purpose of this review is to highlight developments in self-assembled nanostructured materials(i.e.,mesoporous and nanoparticle-based materials)and their catalytic applications.Since there are many available reviews of metal-based nanoparticles as catalysts,this review will mainly focus on self-assembled oxide-based catalytic materials.The content includes:(1)design and synthetic strategies for self-assembled mesoporous catalysts,(2)polyoxometalate(POM)-based nanocatalysts,(3)dendrimer-based nanocatalysts,and(4)shaped nanomaterials and catalytic applications.We show that controlled assembly of molecules,crystalline seeds,and nano building blocks into organized mesoscopic structures or controlled morphologies is an effective approach for tailoring porosities of heterogeneous catalysts and controlling their catalytic activities.

A self-assembling prodrug nanosystem to enhance metabolic stability and anticancer activity of gemcitabine

Self-assembly is a powerful approach in molecular engineering for biomedical applications,in particu-lar for creating self-assembling prodrugs.Here,we report a self-assembling prodrug of the anticancer drug gemcitabine(Gem)based on amphiphilic dendrimer approach.The prodrug reported in this study demonstrates high drug loading(40%)and robust ability to self-assemble into small nanomicelles,which increase the metabolic stability of Gem and enable entry into cells via endocytosis,hence bypassing transport-mediated uptake.In addition,this prodrug nanosystem exhibited an effective pH-and enzyme-responsive release of Gem,resulting in enhanced anticancer activity and reduced toxicity.Harboring ad-vantageous features of both prodrug-and nanotechnology-based drug delivery,this self-assembling Gem prodrug nanosystem constitutes a promising anticancer candidate.This study also offers new perspectives of the amphiphilic dendrimer nanoplatforms for the development of self-assembling prodrugs.

以卟啉为中心核的树枝状化合物

以卟啉为中心核的树枝状化合物具有特殊的物理、化学及光电性能,其中一个重要特性是具有优良的能量和电子转移性能,近年来研究人员合成了一系列新型的以卟啉为中心核的树枝状化合物,这些化合物在许多领域有着潜在的应用前景。本文综述了近几年来以卟啉为中心核的树枝状化合物的最新研究结果,介绍了一些具有代表性的新型化合物,概述了部分化合物的合成方法及性能,这些化合物由于其结构改变带来的性能变化,分别在光收集材料、发光材料、光动力学疗法、催化剂、传感器等领域有着潜在的应用前景。最后展望了此类化合物的发展方向。