Nonperipherally Octa(butyloxy)‐Substituted Phthalocyanine Derivatives with Good Crystallinity: Effects of Metal–Ligand Coordination on the Molecular Structure,Internal Structure,and Dimensions of Self‐Assembled Nanostructures

To investigate the effects of metal–ligand coordination on the molecular structure, internal structure, dimensions, and morphology of self‐assembled nanostructures, two nonperipherally octa(alkoxyl)‐substituted phthalocyanine compounds with good crystallinity, namely, metal‐free 1,4,8,11,15,18,22,25‐octa(butyloxy)phthalocyanine H₂Pc(α‐OC₄H₉)₈ ( 1 ) and its lead complex Pb[Pc(α‐OC₄H₉)₈] ( 2 ), were synthesized. Single‐crystal X‐ray diffraction analysis revealed the distorted molecular structure of metal‐free phthalocyanine with a saddle conformation. In the crystal of 2 , two monomeric molecules are linked by coordination of the Pb atom of one molecule with an aza‐nitrogen atom and its two neighboring oxygen atoms from the butyloxy substituents of another molecule, thereby forming a Pb‐connected pseudo‐double‐decker supramolecular structure with a domed conformation for the phthalocyanine ligand. The self‐assembling properties of 1 and 2 in the absence and presence of sodium ions were comparatively investigated by scanning electronic microscopy (SEM), spectroscopy, and X‐ray diffraction techniques. Intermolecular π–π interactions between metal‐free phthalocyanine molecules led to the formation of nanoribbons several micrometers in length and with an average width of approximately 100 nm, whereas the phthalocyaninato lead complex self‐assembles into nanostructures also with the ribbon morphology and micrometer length but with a different average width of approximately 150 nm depending on the π–π interactions between neighboring Pb‐connected pseudo‐double‐decker building blocks. This revealed the effect of the molecular structure (conformation) associated with metal–ligand (Pb? N_isoindole, Pb? N_aza, and Pb? O_butyloxy) coordination on the dimensions of the nanostructures. In the presence of Na⁺, additional metal–ligand (Na? N_aza and Na? O_butyloxy) coordination bonds formed between sodium atoms and aza‐nitrogen atoms and the neighboring butyloxy oxygen atoms of two metal‐free phthalocyanine molecules cooperate with the intrinsic intermolecular π–π interactions, thereby resulting in an Na‐connected pseudo‐double‐decker building block with a twisted structure for the phthalocyanine ligand, which self‐assembles into twisted nanoribbons with an average width of approximately 50 nm depending on the intertetrapyrrole π–π interaction. This is evidenced by the X‐ray diffraction analysis results for the resulting aggregates. Twisted nanoribbons with an average width of approximately 100 nm were also formed from the lead coordination compound 2 in the presence of Na⁺ with a Pb‐connected pseudo‐double‐decker as the building block due to the formation of metal–ligand (Na? N_aza and Na? O_butyloxy) coordination bonds between additionally introduced sodium ions and two phthalocyanine ligands of neighboring pseudo‐double‐decker building blocks.     

A Self‐Assembled Superhydrophobic Electrospun Carbon–Silica Nanofiber Sponge for Selective Removal and Recovery of Oils and Organic Solvents

An oil spill needs timely cleanup before it spreads and poses serious environmental threat to the polluted area. This always requires the cleanup techniques to be efficient and cost‐effective. In this work, a lightweight and compressible sponge made of carbon–silica nanofibers is derived from electrospinning nanotechnology that is low‐cost, versatile, and readily scalable. The fabricated sponge has high porosity (>99 %) and displays ultra‐hydrophobicity and superoleophilicity, thus making it a suitable material as an oil adsorbent. Owing to its high porosity and low density, the sponge is capable of adsorbing oil up to 140 times its own weight with its sorption rate showing solution viscosity dependence. Furthermore, sponge regeneration and oil recovery are feasible by using either cyclic distillation or mechanical squeezing.     

Oligomeric Hydrogels Self‐Assembled from Reduction‐Controlled Condensation

Polymer hydrogels and small‐molecule‐based (SMB) supramolecular hydrogels have been widely explored. But oligomeric hydrogels have remained a challenge because synthetic difficulties of the oligomers and control of their amphiphilicities. Reported herein is the rational design of two precursors Cys(SEt)‐Lys‐CBT ( 1 ) and (Cys‐Lys‐CBT)₂ ( 2 ) (CBT=2‐cyano‐6‐aminobenzothiazole) and the use of a biocompatible condensation to prepare oligomeric hydrogels. Glutathione reduction of 1 or 2 yields the same gelator Cys‐Lys‐CBT ( 3 ) which condenses with each other to yield amphiphilic cyclic oligomers. The oligomers instantly self‐assemble into nanofibers and form oligomeric hydrogels with similar mechanic properties. Chemical analyses indicated that the major condensation product in both two hydrogels is a cyclic dimer. Considering its biocompatibility, optimal mechanical strength, and biodegradability, we believe that our oligomeric hydrogel might be useful for long‐term drug delivery in the future.     

Gold‐Nanoparticle‐Mediated Jigsaw‐Puzzle‐like Assembly of Supersized Plasmonic DNA Origami

DNA origami has rapidly emerged as a powerful and programmable method to construct functional nanostructures. However, the size limitation of approximately 100 nm in classic DNA origami hampers its plasmonic applications. Herein, we report a jigsaw‐puzzle‐like assembly strategy mediated by gold nanoparticles (AuNPs) to break the size limitation of DNA origami. We demonstrated that oligonucleotide‐functionalized AuNPs function as universal joint units for the one‐pot assembly of parent DNA origami of triangular shape to form sub‐microscale super‐origami nanostructures. AuNPs anchored at predefined positions of the super‐origami exhibited strong interparticle plasmonic coupling. This AuNP‐mediated strategy offers new opportunities to drive macroscopic self‐assembly and to fabricate well‐defined nanophotonic materials and devices.     

Self‐Assembled Vesicles with Functionalized Membranes

Biological membranes play a key role for the function of living organisms. Thus, many artificial systems have been designed to mimic natural cell membranes and their functions. A useful concept for the preparation of functional membranes is the embedding of synthetic amphiphiles into vesicular bilayers. The dynamic nature of such noncovalent assemblies allows the rapid and simple development of bio‐inspired responsive nanomaterials, which find applications in molecular recognition, sensing or catalysis. However, the complexity that can be achieved in artificial functionalized membranes is still rather limited and the control of their dynamic properties and the analysis of membrane structures down to the molecular level remain challenging.     

Self‐Assembled Organic Microtubes from Amphiphilic Molecules

Getting the sizes sorted out : In recent years, there have been increasing numbers of reports about self‐assembled nano‐ or microtubular structures because of their potential uses in a variety of technical applications, which are largely determined by the tube sizes. This Focus Review highlights microsized self‐assembled organic tubular structures formed in aqueous solutions and organic solvents.

     

Convenient and Mild Epoxidation of Alkenes Using Heterogeneous Cobalt Oxide Catalysts

A general epoxidation of aromatic and aliphatic olefins has been developed under mild conditions using heterogeneous Co_xO_y–N/C (x=1,3; y=1,4) catalysts and tert‐butyl hydroperoxide as the terminal oxidant. Various stilbenes and aliphatic alkenes, including renewable olefins, and vitamin and cholesterol derivatives, were successfully transformed into the corresponding epoxides with high selectivity and often good yields. The cobalt oxide catalyst can be recycled up to five times without significant loss of activity or change in structure. Characterization of the catalyst by XRD, TEM, XPS, and EPR analysis revealed the formation of cobalt oxide nanoparticles with varying size (Co₃O₄ with some CoO) and very few large particles with a metallic Co core and an oxidic shell. During the pyrolysis process the nitrogen ligand forms graphene‐type layers, in which selected carbon atoms are substituted by nitrogen.     

Tunable Bacterial Agglutination and Motility Inhibition by Self‐Assembled Glyco‐Nanoribbons

We explored a method of controlling bacterial motility and agglutination by using self‐assembled carbohydrate‐coated β‐sheet nanoribbons. To this aim, we synthesized triblock peptides that consist of a carbohydrate, a polyethylene glycol (PEG) spacer, and a β‐sheet‐forming peptide. An investigation into the effect of PEG‐spacer length on the self‐assembly of the triblock peptides showed that the PEG should be of sufficiently length to stabilize the β‐sheet nanoribbon structure. It was found that the stabilization of the nanoribbon led to stronger activity in bacterial motility inhibition and agglutination, thus suggesting that antibacterial activity can be controlled by the stabilization strategy. Furthermore, another level of control over bacterial motility and agglutination was attained by co‐assembly of bacteria‐specific and ‐nonspecific supramolecular building blocks. The nanoribbon specifically detected bacteria after the encapsulation of a fluorescent probe. Moreover, the detection sensitivity was enhanced by the formation of bacterial clusters. All these results suggest that the carbohydrate‐coated β‐sheet nanoribbons can be developed as promising agents for pathogen capture, inactivation, and detection, and that the activity can be controlled at will.     

Selective Lanthanides Sequestration Based on a Self‐Assembled Organosilica

In this paper, we investigate the cation‐exchange properties of a self‐assembled hybrid material towards trivalent ions, lanthanides (La³⁺, Eu³⁺, Gd³⁺, Yb³⁺) and Fe³⁺. The bis‐zwitterionic lamellar material was prepared by sol–gel process from only 3‐aminopropyltriethoxysilane (APTES), succinic anhydride, and ethylenediamine. In ethanol heated under reflux, the exchange ethylenediammonium versus Ln³⁺ proved to be complete by complexometry measurements and elemental analyses, one Cl^? ion per one Ln^III remaining as expected for charge balance. In aqueous solution at 20 °C, the material was found to be selective towards lanthanide in spite of the similarity of their ionic radii. The cation uptake depends on the nature of the salt, the difference between two lanthanides reaching up to 20 % in some cases. Finally, ion‐exchange reaction with FeCl₃ was chosen as a probe to get more information on the material after incorporation of trivalent ions. Based on Mössbauer spectroscopic investigations on the resulting material in conjunction with the XRD analysis of materials containing trivalent ions, a structural model was proposed to describe the incorporation of trivalent ions by exchange reaction within the original zwitterionic material.     

Self‐Assembled Discrete Molecules for Sensing Nitroaromatics

Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO₂‐containing electron‐deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron‐rich self‐assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several π‐electron‐rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal–ligand coordination‐bonding interactions, with enough internal space to accommodate electron‐deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives.     

Heterogeneous CuII‐Catalysed Solvent‐Controlled Selective N‐Arylation of Cyclic Amides and Amines with Bromo‐iodoarenes

A selective N‐arylation of cyclic amides and amines in DMF and water, respectively, catalysed by Cu^II/Al₂O₃ has been achieved. This protocol has been employed for the synthesis of a library of arenes bearing a cyclic amide and an amine moiety at two ends, including a few scaffolds of therapeutic importance. The mechanism has been established based on detailed electron paramagnetic resonance (EPR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), UV diffuse reflectance spectroscopy (DRS) and inductively coupled plasma‐mass spectrometry (ICP‐MS) studies of the catalyst at different stages of the reaction. The Cu^II/Al₂O₃ catalyst was recovered and recycled for subsequent reactions.