Modulation of supramolecular structure by stepwise removal of tert-butyl groups from tetraazaperopyrene derivatives on Ag(111).

Tert-butyl functional groups can modulate the self-assembly behavior of organic molecules on surfaces. However, the precise construction of supramolecular architectures through their controlled thermal removal remains a challenge. Herein, we precisely controlled the removal amount of tert-butyl groups in tetraazaperopyrene derivatives by stepwise annealing on Ag(111). The evolution of 4tBu-TAPP supramolecular self-assembly from the grid-like structure composed of 3tBu-TAPP through the honeycomb network formed by 2tBu-TAPP to the one-dimensional chain co-assembled by tBu-TAPP and TAPP was successfully realized. This series of supramolecular nanostructures were directly visualized by high resolution scanning tunneling microscopy. Tip manipulation and density functional theory calculations show that the formation of honeycomb network structure can be attributed to the van der Waals interactions, N-Ag-N coordination bonds, and weak C-H⋯N hydrogen bonds. Further addition of two tert-butyl groups (6tBu-TAPP) leads to a completely different assembly evolution, due to the fact that the additional tert-butyl groups affect the molecular adsorption behavior and ultimately induce desorption. This work can possibly be exploited in constructing stable and long-range ordered nanostructures in surface-assisted systems, which can also promote the development of nanostructures in functional molecular devices.

Optimal search mapping among sensors in heterogeneous smart homes.

There are huge differences in the layouts and numbers of sensors in different smart home environments. Daily activities performed by residents trigger a variety of sensor event streams. Solving the problem of sensor mapping is an important prerequisite for the transfer of activity features in smart homes. However, it is common practice among most of the existing approaches that only sensor profile information or the ontological relationship between sensor location and furniture attachment are used for sensor mapping. The rough mapping seriously restricts the performance of daily activity recognition. This paper presents a mapping approach based on the optimal search for sensors. To begin with, a source smart home that is similar to the target one is selected. Thereafter, sensors in both source and target smart homes are grouped by sensor profile information. In addition, sensor mapping space is built. Furthermore, a small amount of data collected from the target smart home is used to evaluate each instance in sensor mapping space. In conclusion, Deep Adversarial Transfer Network is employed to perform daily activity recognition among heterogeneous smart homes. Testing is conducted using the public CASAC data set. The results have revealed that the proposed approach achieves a 7-10% improvement in accuracy, 5-11% improvement in precision, and 6-11% improvement in F1 score, compared with the existing methods.

On-Surface Synthesis of a Nitrogen-Doped Graphene Nanoribbon with Multiple Substitutional Sites.

Doped graphene nanoribbons (GNRs) with heteroatoms are a principal strategy to fine-tune the electronic structures of GNRs for future device applications. Here, we successfully synthesized the N=9 nitrogen-doped armchair GNR on the Au(111) surface. Due to the flexibility of precursor molecules, three different covalent bonds (C-C, C-N, N-N) are formed in the GNR backbone. Scanning tunneling spectroscopy analysis together with band structure calculations reveals that the band gap of the N-9-AGNRs (C-C) will be enlarged compared to pristine 9-AGNRs, and the C-N bond and N-N bond at the isolated site of N-9-AGNR (C-C) will introduce new defect states near the Fermi level. DFT calculations reveal that the electronic structure of N-9-AGNR (C-C) shows semiconductor character, while N-9-AGNR (C-N) and N-9-AGNR (N-N) display metallic character. Our results provide a promising route for creating more complex molecular heterostructures with tunable band gaps, which may be useful for future molecular electronics and memory device applications.

Identification and electronic characterization of four cyclodehydrogenation products of H2TPP molecules on Au(111).

C-H bond activation and dehydrogenative coupling reactions have always been significant approaches to construct microscopic nanostructures on surfaces. By using scanning tunneling microscopy/spectroscopy (STM/STS) and non-contact atomic force microscopy (nc-AFM) combined with density functional theory (DFT), we systematically characterized the atomically precise topographies and electronic properties of H2TPP cyclodehydrogenation products on Au(111). Through surface-assisted thermal excitation, four types of cyclodehydrogenation products were obtained and clearly resolved in the nc-AFM images. The electronic characterization depicts the predominant resonances and their spatial distributions of the four products.

On-surface synthesis of one-type pore single-crystal porous covalent organic frameworks.

Employing a 1,3,5-tris(4-bromophenyl)benzene precursor as a building block, we successfully fabricate large-scale, non-multihole and single-layer pCOFs on the Ag(111) surface in a controllable manner via the on-surface reaction. We reveal that two main factors, the heating rate and growth temperature, have a strong impact on the size and quality of the pCOFs by STM. Furthermore, the band gap of the pCOFs has been further measured to be approximately 3.01 eV.

A novel humanized anti-tumor necrosis factor-related apoptosis-inducing ligand-R2 monoclonal antibody induces apoptotic and autophagic cell death.

It is well known that the tumor necrosis factor-related apoptosis-inducing ligand (TRAIL/TNFSF10) is specifically expressed in various tumor cells, but less or no expression in most normal tissues and cells. While TRAIL engages with its native death receptors, TRAIL receptor 1 (TRAIL-R1) or 2 (TRAIL-R2), usually elicits the tumor cell death by apoptosis. In this study, we report that a novel humanized monoclonal antibody against TRAIL-R2 (named as zaptuzumab) well remain the biological activity of the parental mouse antibody AD5-10 inducing cell death in various cancer cells, but little effect on normal cells. Zaptuzumab also markedly inhibited the tumor growth in the mouse xenograft of NCI-H460 without toxicity to the liver and kidney, and the efficacy of tumor suppression was increased significantly while it combined with cis-dichlorodiamineplatinum. Especially, 131 I-labeled zaptuzumab injected into mouse tail vein specifically targeted to the xenograft of the lung cancer cells. Confocal analysis showed that zaptuzumab bound with TRAIL-R2 on cell surface could be quickly internalized and transferred into the lysosome. Furthermore, zaptuzumab possessed a high level of antibody-dependent cytotoxicity as well as complement-dependent cytotoxicity. Study on the mechanisms of cell death induced by zaptuzumab showed that it efficiently induced both caspase-dependent apoptosis and autophagic cell death. These data suggest that the humanized anti-TRAIL-R2 monoclonal antibody or the second generation of the antibody may have an important clinical usage for cancer immunotherapy. © 2017 IUBMB Life, 69(9):735-744, 2017.