Metal-free carbazole-thiophene photosensitizers designed for a dye-sensitized H2-evolving photocatalyst in Z-scheme water splitting.

Dye-sensitized photocatalysts with molecular dyes and widegap semiconductors have attracted attention because of their design flexibility, for example, tunable light absorption for visible-light water splitting. Although organic dyes are promising candidates as metal-free photosensitizers in dye-sensitized photocatalysts, their efficiency in H2 production has far been unsatisfactory compared to that of metal-complex photosensitizers, such as Ru(II) tris-diimine-type complexes. Here, we demonstrate the substantial improvement of carbazole-thiophene-based dyes used for dye-sensitized photocatalysts through systematic molecular design of the number of thiophene rings, substituents in the thiophene moiety, and the anchoring group. The optimized carbazole-thiophene dye-sensitized layered niobate exhibited a quantum efficiency of 0.3% at 460 nm for H2 evolution using a redox-reversible I- electron donor, which is six-times higher than that of the best coumarin-based metal-free dye reported to date. The dye-sensitized photocatalyst also facilitated overall water splitting when combined with a WO3-based O2-evolving photocatalyst and an I3-/I- redox shuttle mediator. The present metal-free dye provided a high dye-based turnover frequency for water splitting, comparable to that of the state-of-the-art Ru(II) tris-diimine-type photosensitizer, by simple adsorption onto a layered niobate. Thus, this study highlights the potential of metal-free organic dyes with appropriate molecular designs for the development of efficient water splitting.

Unlocking the Drug Potential of the Bryostatin Family: Recent Advances in Product Synthesis and Biomedical Applications.

Bryostatins are a class of naturally occurring macrocyclic lactones with a unique fast developing portfolio of clinical applications, including treatment of AIDS, Alzheimer's disease, and cancer. This comprehensive account summarizes the recent progress (2014-present) in the development of bryostatins, including their total synthesis and biomedical applications. An emphasis is placed on the discussion of bryostatin 1, the most-studied analogue to date. This review highlights the synthetic and biological challenges of bryostatins and provides an outlook on their future development.

Greener liquid-phase synthesis and the ACE inhibitory structure-activity relationship of an anti-SARS octapeptide.

A high-efficiency strategy for resin-free and large scale liquid phase synthesis of the anti-SARS octapeptide AVLQSGFR is described. Herein, tri(4'-diphenylphosphonyloxylbenzoyl phenyl)phosphate (TDPBP) derivatives were designed as C-terminal supports to aid octapeptide intermediate purification without the need for chromatographic separation. Furthermore, the ACE inhibitory structure-activity relationship (SAR) of the anti-SARS octapeptide and its alanine-scanning analogues was systematically studied by in vitro assay and 3D-QSAR via molecular docking. This paper provides a new strategy for the development of peptide-based drugs. Simultaneously, a study on the ACE inhibition and structure-activity relationship of the anti-SARS octapeptide also lays a foundation for further understanding how the anti-SARS octapeptide acts as an ACE inhibitor.

Enhancing adsorption capacity while maintaining specific recognition performance of mesoporous silica: a novel imprinting strategy with amphiphilic ionic liquid as surfactant.

In order to facilitate the broad applications of molecular recognition materials in biomedical areas, it is critical to enhance their adsorption capacity while maintaining their excellent recognition performance. In this work, we designed and synthesized well-defined peptide-imprinted mesoporous silica (PIMS) for specific recognition of an immunostimulating hexapeptide from human casein (IHHC) by using amphiphilic ionic liquid as the surfactant to anchor IHHC via a combination of one-step sol-gel method and docking oriented imprinting approach. Thereinto, theoretical calculation was employed to reveal the multiple binding interactions and dual-template configuration between amphiphilic ionic liquid and IHHC. The fabricated PIMS was characterized and an in-depth analysis of specific recognition mechanism was conducted. Results revealed that both adsorption and recognition capabilities of PIMS far exceeded that of the NIMS's. More significantly, the PIMS exhibited a superior binding capacity (60.5 mg g-1), which could increase 18.9% than the previous work. The corresponding imprinting factor and selectivity coefficient could reach up to 4.51 and 3.30, respectively. The PIMS also possessed lickety-split kinetic binding for IHHC, where the equilibrium time was only 10 min. All of these merits were due to the high surface area and the synergistic effect of multiple interactions (including hydrogen bonding, π-π stacking, ion-ion electrostatic interactions and van der Waals interactions, etc) between PIMS and IHHC in imprinted sites. The present work suggests the potential application of PIMS for large-scale and high-effective separation of IHHC, which may lead to their broad applications in drug/gene deliver, biosensors, catalyst and so on.

Synthesis of methoxy-substituted picenes: substitution position effect on their electronic and single-crystal structures.

A series of picenes having methoxy groups was synthesized through Pd-catalyzed Suzuki-Miyaura couplings or Wittig reaction/intramolecular cyclization sequences, and their physicochemical properties and single-crystal structures were evaluated. The substitution position effects between the outer 1,12-, 2,11-, and 4,9-position and the inner 3,10-position are quite different; the former showed the same electronic structure as that of picene, but the latter results in a HOMO geometry different from those of picene and other methoxy picenes. In addition, crystal structures of four types of methoxy-substituted picenes 4a-c,e strongly depend on their substitution position and number of methoxy groups, which dramatically changes the structures from the fully anisotropic 1D π-stacked structure to a unique 3D herringbone structure due to steric hindrance of methoxy groups. The calculations of transfer integrals based on their single-crystal structures reveal that the methoxy picenes have intermolecular overlaps less effective than that of the parent nonsubstituted picene. These results are attributed not only to the packing structure but also to electronic structures such as the HOMO distribution. The preliminary OFET of the representative 4c,e showed hole mobilities significantly lower than that of picene due to their less effective intermolecular overlaps, as predicted by the calculated transfer integrals.

A facile and practical copper powder-catalyzed, organic solvent- and ligand-free Ullmann amination of aryl halides.

A facile and practical method that the copper powder-catalyzed Ullmann amination of aryl halides with aqueous methylamine under organic solvent- and ligand-free condition at 100 °C and in air gave N-arylamines as sole products in good to excellent yields. The presence of a small amount of air is essential. Other aliphatic primary amines show good to very high reactivity. Secondary amines and aniline are not reactive. Sensitive substituents (i.e., CHO, MeCO, CN and Cl) are tolerable in the reaction.

Flexible Diodes/Transistors Based on Tunable p-n-Type Semiconductivity in Graphene/Mn-Co-Ni-O Nanocomposites.

We report a novel Mn-Co-Ni-O (MCN) nanocomposite in which the p-type semiconductivity of Mn-Co-Ni-O can be manipulated by addition of graphene. With an increase of graphene content, the semiconductivity of the nanocomposite can be tuned from p-type through electrically neutral to n-type. The very low effective mass of electrons in graphene facilitates electron tunneling into the MCN, neutralizing holes in the MCN nanoparticles. XPS analysis shows that the multivalent manganese ions in the MCN nanoparticles are chemically reduced by the graphene electrons to lower-valent states. Unlike traditional semiconductor devices, electrons are excited from the filled graphite band into the empty band at the Dirac points from where they move freely in the graphene and tunnel into the MCN. The new composite film demonstrates inherent flexibility, high mobility, short carrier lifetime, and high carrier concentration. This work is useful not only in manufacturing flexible transistors, FETs, and thermosensitive and thermoelectric devices with unique properties but also in providing a new method for future development of 2D-based semiconductors.

Liquid-Phase Total Synthesis of Plecanatide Aided by Diphenylphosphinyloxyl Diphenyl Ketone (DDK) Derivatives.

Plecanatide is an oral guanylate cyclase-C agonist for the treatment of gastrointestinal disorders. The large-scale supply of plecanatide is restrained primarily by its industrial manufacture. Herein we developed diphenylphosphinyloxyl diphenyl ketone (DDK) derivatives as greener supports with unique precipitation-inducing properties to aid the liquid-phase total synthesis of plecanatide without the use of chromatography. Plecanatide could be obtained in high yield, and the ultimately sheared DDK derivative residue could be directly recycled or regenerated for reuse.

Synergetically understanding the interaction between nano/microspheres and peptide for controllable drug loading via experimental and theoretical approaches.

In this paper we systematically investigate the loading capacity of raspberry-like nano/microspheres with highly cross-linked structure for the peptide, immunostimulating hexapeptide from human (IHH), by integrating both experimental and simulation efforts. The experimental results indicate that the loading capacities of raspberry-like nano/microspheres with different functionalized chains vary drastically. To provide theoretical insights into the observed phenomenon, the typical raspberry-like nano/microspheres were simplified as effective functionalized groups, thereby the interactions between them and IHH were accurately calculated by ab initio method. The ab initio results agree well with the experimental observations, and the underlying binding mechanism is analyzed in great details. It is shown that hydrogen bonding plays an important role and the binding affinity strongly depends on the functionalized motifs. Therefore, this work provides insightful guidance to controlling the drug loading by design of the functionalized surface of nanomaterials.

Synthesis of substituted picenes through Pd-catalyzed cross-coupling reaction/annulation sequences and their physicochemical properties.

A novel and versatile synthetic method for picene derivatives is developed using the Pd-catalyzed intramolecular double cyclization of the corresponding 2,3-bis[(1Z)-2-phenylethenyl]-1,4-dichlorobenzenes, which are readily prepared by Suzuki-Miyaura cross-coupling reactions of polyhalobenzenes with (Z)-arylethenylboronates. The physical properties of the obtained picenes can be modified via introducing a variety of functional groups to the picene framework. All compounds are investigated by UV-vis and fluorescence spectroscopic measurements, CV, and DFT calculations as well as X-ray diffraction analysis.