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Tolyporphins were discovered some 30 years ago as part of a global search for antineoplastic compounds from cyanobacteria. To date, the culture HT-58-2, comprised of a cyanobacterium–microbial consortium, is the sole known producer of tolyporphins. Eighteen tolyporphins are now known—each is a free base tetrapyrrole macrocycle with a dioxobacteriochlorin (14), oxochlorin (3), or porphyrin (1) chromophore. Each compound displays two, three, or four open β-pyrrole positions and two, one, or zero appended C-glycoside (or –OH or –OAc) groups, respectively; the appended groups form part of a geminal disubstitution motif flanking the oxo moiety in the pyrroline ring. The distinct structures and repertoire of tolyporphins stand alone in the large pigments-of-life family. Efforts to understand the cyanobacterial origin, biosynthetic pathways, structural diversity, physiological roles, and potential pharmacological properties of tolyporphins have attracted a broad spectrum of researchers from diverse scientific areas. The identification of putative biosynthetic gene clusters in the HT-58-2 cyanobacterial genome and accompanying studies suggest a new biosynthetic paradigm in the tetrapyrrole arena. The present review provides a comprehensive treatment of the rich science concerning tolyporphins.

 

Abstract Bond breaking and forming are essential components of chemical reactions. Recently, the structure and formation of covalent bonds in single molecules have been studied by non-contact atomic force microscopy (AFM). Here, we report the details of a single dative bond breaking process using non-contact AFM. The dative bond between carbon monoxide and ferrous phthalocyanine was ruptured via mechanical forces applied by atomic force microscope tips; the process was quantitatively measured and characterized both experimentally and via quantum-based simulations. Our results show that the bond can be ruptured either by applying an attractive force of ~150 pN or by a repulsive force of ~220 pN with a significant contribution of shear forces, accompanied by changes of the spin state of the system. Our combined experimental and computational studies provide a deeper understanding of the chemical bond breaking process. 

Deterministic assembly of metallic nanoparticles ( e.g. gold nanoparticles) into prescribed configurations has promising applications in many fields such as biosensing and drug delivery. DNA-directed bottom-up assembly has demonstrated unparalleled capability to precisely organize metallic nanoparticles into assemblies of designer configurations. However, the fabrication of assemblies comprising delicate nanoparticle arrangements, especially across large dimensions ( e.g. micron size), has remained challenging. In this report, we have designed DNA origami hexagon tiles that are capable of assembling into higher-order networks of honeycomb arrays or tubes with dimensions up to several microns. The versatile addressability of the unit tile enables precise and periodic positioning of nanoparticles onto these higher-order DNA origami frame structures. Overall, we have constructed a series of 9 gold nanoparticle architectures with programmable configurations ranging from nanometer-sized clusters to micrometer-sized lattices. We believe these architectures shall hold great application potential in numerous biomedical fields. 

The emerging connected-vehicle technology provides a new dimension for developing more intelligent traffic control algorithms for signalized intersections. An important challenge for scheduling in networked transportation systems is the switchover delay caused by the guard time before any traffic signal change. The switch-over delay can result in significant loss of system capacity and hence needs to be accommodated in the scheduling design. To tackle this challenge, we propose a distributed online scheduling policy that extends the wellknown Max-Pressure policy to address switch-over delay by introducing a bias factor favoring the current schedule. We prove that the proposed policy is throughput-optimal with switch-over delay. Furthermore, the proposed policy remains optimal when there are both connected signalized intersections and conventional fixed-time ones in the system. With connected-vehicle technology, the proposed policy can be easily incorporated into the current transportation systems without additional infrastructure. Through extensive simulation in VISSIM, we show that our policy indeed outperforms the existing popular policies.