Yaming Zhou

Quadruple Switching of Pleated Foldamers of Tetrathiafulvalene–Bipyridinium Alternating Dynamic Covalent Polymers

Two dynamic covalent polymers P1 and P2 were prepared by alternately linking electron-rich tetrathiafulvalene (TTF) and electron-deficient bipyridinium (BIPY(2+) ) through hydrazone bonds. In acetonitrile, the polymers were induced by intramolecular donor-acceptor interactions to form pleated foldamers, which unfolded upon oxidation of the TTF units to the radical cation TTF(.+) . Reduction of the BIPY(2+) units to BIPY(.+) led to the formation of another kind of pleated secondary structures, which are stabilized by intramolecular dimerization of the BIPY(.+) units. The diradical dicationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT(2(.+)) ) could further force the folded structures to unfold by including the BIPY(.+) units of the polymers. Upon oxidation of the BIPY(.+) units of the cyclophane and polymers to BIPY(2+) , the first folded state was regenerated. Switching or conversion between the four conformational states was confirmed by UV/Vis spectroscopic experiments.

Bipyridinium radical cation dimerization-driven polymeric pleated foldamers and a homoduplex that undergo ion-tuned interconversion

Four oligo(ethylene glycol)-linked bipyridinium (BIPY2+) polymers have been prepared via forming hydrazone bonds. Reducing the BIPY2+ units into a radical cation (BIPY˙+) with zinc induces the polymers to fold into pleated states or form a duplex via BIPY˙+ dimerization. The duplex and foldamer can convert into each other by alternately adding NH4+ and NEt3.

A self-catenated rob-type porous coordination polymer constructed from triazolate and carboxylate ligands: fluorescence response to the reversible phase transformation

A flexible structure of {[Zn2(dmtrz)2(L1)]·6H2O}n (MAC-11) (Hdmtrz = 3,5-dimethyl-1H,1,2,4-triazole, H2L1 = (E)-4,4′-stilbenedicarboxylic acid), which is a self-catenated rob-type net built of two-dimensional [Zn(dmtrz)] layers pillared by L1 ligands, has been solvothermally synthesized. It shows an interesting thermo/water-induced reversible phase transformation accompanied by a photoluminescence response from 418 nm to 453 nm. Based on an iso-framework of {[Zn2(dmtrz)2(L2)]·4H2O}n (MAC-13, H2L2 = (E)-azobenzene-4,4′-dicarboxylic acid), a pcu-type framework of {[Zn2(trz)2(L1)]·4H2O}n (MAC-14, Htrz = 1H, 1,2,4-triazole), and a layered structure of [Zn(dmtrz)(HCOO)], a possible mechanism for the photoluminescence response to the reversible phase transformation for MAC-11 was also proposed.

Cation-Exchange Approach to Tuning the Flexibility of a Metal–Organic Framework for Gated Adsorption

Achieving tailorable gated adsorption by tuning the dynamic behavior of a host porous material is of great interest because of its practical application in gas adsorption and separation. Here we devise a unique cation-exchange approach to tune the dynamic behavior of a flexible anionic framework, [Zn2(bptc)(datrz)]- (denoted as MAC-6, where H4bptc = [1,1-biphenyl]-3,3,5,5-tetracarboxylic acid and Hdatrz = 3,5-diamine-1H-1,2,4-triazole), so as to realize the tailorable gated adsorption. The CO2 adsorption amount at 273 K can be enhanced by exchanging the counterion of protonated dimethylamine (HDMA+) with tetraethylammonium (TEA+), tetrabutylammonium (TBA+), and tetramethylammonium (TMA+), where the adsorption behavior is transferred from nongated to gated adsorption. Interestingly, the Pgo for gate-opening adsorption can be further tuned from 442 to 331 mmHg by simply adjusting the ratio of HDMA+ and TMA+. The origin of this unique tunable property, as revealed by X-ray diffraction experiments and structure models, is rooted at the cation-responsive characteristic of this flexible framework.

Integrating Zeolite-Type Chalcogenide with Titanium Dioxide Nanowires for Enhanced Photoelectrochemical Activity

Developing photoanodes with efficient visible-light harvesting and excellent charge separation still remains a key challenge in photoelectrochemical water splitting. Here zeolite-type chalcogenide CPM-121 is integrated with TiO2 nanowires to form a heterostructured photoanode, in which crystalline CPM-121 particles serve as a visible light absorber and TiO2 nanowires serve as an electron conductor. Owing to the small band gap of chalcogenides, the hybrid electrode demonstrates obvious absorption in visible-light range. Electrochemical impedance spectroscopy (EIS) shows that electron transport in the hybrid electrode has been significantly facilitated due to the heterojunction formation. A >3-fold increase in photocurrent is observed on the hybrid electrode under visible-light illumination when it is used as a photoanode in a neutral electrolyte without sacrificial agents. This study opens up a new avenue to explore the potential applications of crystalline porous chalcogenide materials for solar-energy conversion in photoelectrochemistry.

Discovery of a Novel Series of 7-Azaindole Scaffold Derivatives as PI3K Inhibitors with Potent Activity

The phosphoinositide 3-kinase (PI3K) inhibitors potently inhibit the signaling pathway of PI3K/AKT/mTOR, which provides a promising new approach for the molecularly targeted cancer therapy. In this work, a novel series of 7-azaindole scaffold derivatives was discovered by the fragment-based growing strategy. The structure-activity relationship profiles identified that the 7-azaindole scaffold derivatives exhibit potent activity against PI3K at molecular and cellular levels as well as cell proliferation in a panel of human tumor cells.

Preparation of highly dispersed γ-Fe2O3 and GdPO4 co-functionalized mesoporous carbon spheres for dual-mode MR imaging and anti-cancer drug carrying

There is great interest in integration of paramagnetic gadolinium compounds and superparamagnetic iron oxide-based nanoparticles into ordered mesoporous carbon spheres (OMCSs) as a combined platform for T1- and T2-weighted magnetic resonance (MR) imaging and drug carrying. In this work, highly dispersed γ-Fe2O3 and GdPO4 nanoparticle co-functionalized mesoporous carbon spheres were successfully prepared using a 3d-4f heterometallic cluster of [Fe6Gd6(μ3-O)2(CO3)(O3PPh)6(O2CtBu)18] as the precursor. The study reveals that multi-scale confinement effects play a role in concurrent generation of Fe and Gd nanoparticles in the carbon matrix. In addition, dual-mode MR imaging and drug carrying properties were evaluated by in vitro experiments, showing satisfactory r1 and r2 relaxivity values of 8.2 and 94.3 mM-1 s-1, respectively, and doxorubicin hydrochloride (DOX) carrying amount of 132 mg g-1, suggesting potential as a combined system for diagnosis and therapy.

CCDC 906323: Experimental Crystal Structure Determination

Related Article: Weiquan Zhang, Dianpeng Wang, Lin Zhu, Fupeng Zhai, Linhong Weng, Jinyu Sun, Yun Ling, Zhenxia Chen, Yaming Zhou|2016|Dalton Trans.|45|10510|doi:10.1039/C6DT01363E