Internally diketopyrrolopyrrole-bridged bis-anthracene macrocycle: a multifunctional fluorescent platform.

A covalently bridged macrocycle (5) comprising two anthracene strands connected at the lactam positions of a diketopyrrolopyrrole (DPP) chromophore has been constructed. The crystal structure reveals that the central DPP chromophore is wrapped with the externally twisted bis-anthracene macrocycle. The internally bridged macrocycle architecture endows 5 with multifunctional properties.

Planar Chiral Charge-Transfer Cyclophanes: Convenient Synthesis, Circularly Polarized Light-Responsive Photothermal Conversion and Supramolecular Chiral Assembly.

We report herein a series of macrocycles in which the densely π-stacked charge-transfer (CT) donor/acceptor with naphthalenediimides (NDIs) or perylene diimide (PDI) as acceptor moiety pairing various donor moieties are locked by covalent bond. The X-ray crystallography of C8BDT-NDI reveals a short intramolecular π-stacking distance around 3.4 Å and the existence of intermolecular donor/acceptor π-stacking (3.

NIR-II light-powered core-shell prodrug nanomotors enhance cancer therapy through synergistic oxidative stress-photothermo modulation.

Near-infrared-II (NIR-II) photothermal therapy is emerging as a cutting-edge modality for tumor ablation due to its good biosafety, high penetration ability and spatiotemporal controllability. Despite efforts, establishing a link between cellular metabolic regulation and photothermal performance is still promising in synergistic cancer therapy. Herein, we developed a core-shell semiconducting polymer@metal-phenolic network (SP@GFP) nanomotor by assembling diphenol-terminated cisplatin prodrug ligand (cPt-DA) and iron (III) (Fe) through metal coordination on SP particles in the presence of GOx and DSPE-PEG-cRGD, for NIR-II-propelled self-propulsion and synergistic cancer therapy.

Diverse Self-assembly Structures of a Macrocycle Revealed with STM by Adjusting the Solution Concentration.

The macrocyclic molecule [3]C TT-TPA was synthesized by a Stille coupling reaction through alternately connecting 4,7-bisthienyl-2,1,3-thienothiazole and triphenylamine units. The concentration-dependent self-assembly structures of [3]C TT-TPA were explored in liquid/solid interface by scanning tunneling microscopy and density functional theory. After increasing the solution concentration, five different nanostructures were constructed and the molecular packing densities were gradually enhanced.

A shape-persistent arylene ethynylene macrocycle with a multiple acetamide modified cavity: synthesis and gelation.

A new arylene ethynylene macrocycle (AEM) molecule bearing endo-acetamide groups was obtained by a Pd/Cu mediated homo-coupling reaction. Introducing tetraethylene glycol ether as a linkage between two C-shaped fragments substantially improved the final cyclization yield (30%). Concentration-dependent HNMR experiments indicated that strong aggregates formed through H-bonds were observed for this new macrocycle with amide groups in solution.

Superlubricity of Fullerene Derivatives Induced by Host-Guest Assembly.

Fullerenes have been recognized as good candidates for solid lubricants. In this study, the microscale superlubricity of fullerene derivatives was accomplished by the construction of regular host-guest assembly structures. Herein, the host-guest assembly structures of fullerene derivatives were successfully constructed on a highly oriented pyrolytic graphite (HOPG) surface by introducing the macrocycles as the templates and were explicitly revealed by scanning tunneling microscopy (STM).

Pulmonary metastases in newly diagnosed hepatocellular carcinoma: a population-based retrospective study.

Background: Hepatocellular carcinoma (HCC) is a major form of primary liver cancer with steadily increasing incidence for the decades, and has propensity to have extrahepatic metastases, especially pulmonary metastases (PM). This study aimed to investigate temporal incidence trends, treatment, and survival of patients with HCCPM.

Methods: Patients with HCCPM were retrospectively reviewed from 2010 to 2016 in US National Cancer Institute (NCI) Surveillance, Epidemiology, and End Results registry (SEER).

Understanding the Enhanced Open-Circuit Voltage of Polymer Solar Cells Based on a Diketopyrrolopyrrole Small Molecular Acceptor.

In this study, polymer solar cells employing poly(3-hexylthiophene) (P3HT) as a donor and fullerene derivative PCBM (phenyl-C-butyric acid methyl ester) or nonfullerene diketopyrrolopyrrole (DPP)-based small molecule (SF-DPPEH) as an acceptor are investigated. Device based on SF-DPPEH shows a remarkably high V of 1.20 V, whereas analogous device based on PCBM only delivers a V of 0.

Donor-Acceptor Conjugated Macrocycles: Synthesis and Host-Guest Coassembly with Fullerene toward Photovoltaic Application.

Electron-rich (donor) and electron-deficient (acceptor) units to construct donor-acceptor (D-A) conjugated macrocycles were investigated to elucidate their interactions with electron-deficient fullerene. Triphenylamine and 4,7-bisthienyl-2,1,3-benzothiadiazole were alternately linked through acetylene, as the donor and acceptor units, respectively, for pentagonal 3B2A and hexagonal 4B2A macrocycles. As detected by scanning tunneling microscopy, both D-A macrocycles were found to form an interesting concentration-controlled nanoporous monolayer on highly oriented pyrolytic graphite, which could effectively capture fullerene.

Characterization of Pph3-mediated dephosphorylation of Rad53 during methyl methanesulfonate-induced DNA damage repair in .

Genotoxic stress causes DNA damage or stalled DNA replication and filamentous growth in the pathogenic fungus The DNA checkpoint kinase Rad53 critically regulates by phosphorylation effectors that execute the stress response. Rad53 itself is activated by phosphorylation and inactivated by dephosphorylation. Previous studies have suggested that the phosphatase Pph3 dephosphorylates Rad53.

Sds22 participates in Glc7 mediated Rad53 dephosphorylation in MMS-induced DNA damage in Candida albicans.

The protein kinase Rad53 and its orthologs play a fundamental role in regulating the DNA damage checkpoint in eukaryotes. Rad53 is activated by phosphorylation in response to DNA damage and deactivated by dephosphorylation after the damage is repaired. However, the phosphatases involved in Rad53 deactivation are not entirely understood.

Evaluation of heterocycle-modified pentathiophene-based molecular donor materials for solar cells.

Two novel solution-processable acceptor-donor-acceptor (A-D-A)-structured organic small molecules with diketopyrrolopyrrole (DPP) as terminal acceptor units and pentathiophene (PTA) or pyrrole-modified pentathiophene (NPTA) as the central donor unit, namely, DPP2(PTA) and DPP2(NPTA), were designed and synthesized. We examined the effects of changing the central bridging heteroatoms of the five-ring-fused thienoacene core identity from sulfur [DPP2(PTA)] to nitrogen [DPP2(NPTA)] in the small-molecule donor material. Replacement of the bridging atom with a different electronic structure has a visible effect on both the optical and electrical properties: DPP2(NPTA), which contains much more electron-rich pyrrole in the central thienoacene unit, possesses red-shifted absorption and a higher HOMO level relative to DPP2(PTA) with the less electron-rich thiophene in the same position.

2,3,4,5-Tetraphenylsilole-based conjugated polymers: synthesis, optical properties, and as sensors for explosive compounds.

A series of linear 2,5-tetraphenylsilole-vinylene-type polymers were successfully synthesized for the first time. The tetraphenylsilole moieties were linked at their 2,5-positions through a vinylene bridge with p-dialkoxybenzenes to obtain polymer PSVB and with 3,6-carbazole to obtain polymer PSVC. For comparison, 2,5-tetraphenylsilole-ethyne-type polymer PSEB was also synthesized, in which the vinylene bridge of PSVB was replaced with an ethyne bridge.

Phosphole modified pentathienoacene: synthesis, electronic properties and self-assembly.

A series of new ladder π-conjugated materials, phosphole modified pentathienoacene (PO-PTA), are synthesized and characterized. Single-crystal X-ray results demonstrate that methyl-disubstituted PO-PTA forms a face-to-face dimer structure driven by π-π interactions. The investigations of optical properties showed that the oxidized phosphole moiety in this ladder system can effectively narrow the band gap.

Novel ladder π-conjugated materials--sila-pentathienoacenes: synthesis, structure, and electronic properties.

A novel series of ladder π-conjugated materials--sila-pentathienoacenes (Si-PTA) are synthesized and characterized. Crystal structures of the compounds show that the length of alkyl chains substituting on the thiophene ring has a significant influence on molecular packing. A densely packed structure with an interfacial distance of about 3.

Effective tuning of HOMO and LUMO energy levels by p-n diblock and triblock oligomer approaches.

A novel series of oligomers consisting of thiophene as a p-type unit and oxadiazole as an n-type unit were separately synthesized. On the basis of the characterization of photophysical and electrochemical properties, the structure-property relationships of the oligomers were investigated. Cyclic voltammogram studies showed that changing the number of thiophene and oxadiazole units could effectively modulate the electronic properties of the p-n diblock and triblock oligomers.