Hexakis(m-phenylene ethynylene) (m-PE) macrocycles 1-4, sharing the same hydrogen-bonding side chains but having backbones of different electronic properties, are designed to probe the effectiveness of multiple H-bonding interactions in enforcing columnar assemblies. H NMR, absorption, fluorescence, and circular dichroism (CD) spectroscopy indicate that, compared with analogous macrocycles that self-associate based on aromatic stacking which is highly sensitive to the electronic nature of the macrocyclic backbones, macrocycles 1-4 all exhibit strong aggregation down to the micromolar (μM) concentrations in nonpolar solvents. Increasing solvent polarity quickly weakens aggregation. In THF and DMF, the macrocycles exist as free molecules. The observed solvent effects, along with the behavior of 5-F that cannot self-associate via H-bonding, confirm that H-bonding plays the dominating role in driving the self-association of 1-4. The backbone electronic nature does not change the self-assembling pattern common to 1-4. Fluorescence and CD spectra confirm that macrocycles 1-4 assemble anisotropically, forming helical stacks in which adjacent molecules undergo relative rotation to place individual benzene residues in the favorable offset fashion. Columnar alignment of 1-4 is confirmed by atomic force microscopy (AFM), which resolves single tubes consisting of stacked macrocycles. In addition, macrocycles with backbones of different electronic properties are found to undergo heteroassociation, forming hybrid nanotubes. This study has demonstrated the generality of enforcing the alignment of shape-persistent macrocycles, which represents an invaluable addition to the small number of known tubular stacks capable of accommodating structurally varied molecular components and provides self-assembling nanotubes with inner pores allowing ready structural and functional modification.

Supramolecular chemistry in aqueous media is an area with great fundamental and practical significance. To examine the role of multiple noncovalent interactions in controlled assembling and binding behavior in water, the self-association of five water-soluble hexakis­(m-phenylene ethynylene) (m-PE) macrocycles, along with the molecular recognition behavior of the resultant assemblies, is investigated with UV–vis, fluorescence, CD, and NMR spectroscopy, mass spectrometry, and computational studies. In contrast to their different extents of self-aggregation in organic solvents, all five macrocycles remain aggregated in water at concentrations down to the micromolar (μM) range. CD spectroscopy reveals that 1-F 6 and 1-H 6 , two macrocycles carrying chiral side chains and capable of H-bonded self-association, assemble into tubular stacks. The tubular stacks serve as supramolecular hosts in water, as exemplified by the interaction of macrocycles 1-H6 and 2-H 6 and guests G1 through G4, each having a rod-like oligo­(p-phenylene ethynylene) (p-PE) segment flanked by two hydrophilic chains. Fluorescence and 1H NMR spectroscopy revealed the formation of kinetically stable, discrete assemblies upon mixing 2-H 6 and a guest. The binding stoichiometry, determined with fluorescence, 1H NMR, and ESI-MS, reveals that the discrete assemblies are novel pseudorotaxanes, each containing a pair of identical guest molecules encased by a tubular stack. The two guest molecules define the number of macrocyclic molecules that comprise the host, which curbs the “infinite” stack growth, resulting in a tubular stack with a cylindrical pore tailoring the length of the p-PE segment of the bound guests. Each complex is stabilized by the action of multiple noncovalent forces including aromatic stacking, side-chain H-bonding, and van der Waals interactions. Thus, the interplay of multiple noncovalent forces aligns the molecules of macrocycles 1 and 2 into tubular stacks with cylindrical inner pores that, upon binding rod-like guests, lead to tight, discrete, and well-ordered tubular assemblies that are unprecedented in water.

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Chemical vapor deposited graphene suffers from two problems: transfer from metal catalysts to insulators, and photoresist induced degradation during patterning. Both result in macroscopic and microscopic damages such as holes, tears, doping, and contamination, translated into property and yield dropping. We attempt to solve the problems simultaneously. A nickel thin film is evaporated on SiO as a sacrificial catalyst, on which surface graphene is grown. A polymer (PMMA) support is spin-coated on the graphene. During the Ni wet etching process, the etchant can permeate the polymer, making the etching efficient. The PMMA/graphene layer is fixed on the substrate by controlling the surface morphology of Ni film during the graphene growth. After etching, the graphene naturally adheres to the insulating substrate. By using this method, transfer-free, lithography-free and fast growth of graphene realized. The whole experiment has good repeatability and controllability. Compared with graphene transfer between substrates, here, no mechanical manipulation is required, leading to minimal damage. Due to the presence of Ni, the graphene quality is intrinsically better than catalyst-free growth. The Ni thickness and growth temperature are controlled to limit the number of layers of graphene. The technology can be extended to grow other two-dimensional materials with other catalysts.

A method for direct growth of graphene nanowalls (GNWs) on an insulating substrate by plasma enhanced chemical vapor deposition (PECVD) is reported. The effects of growth temperature, plasma power, carbon source concentration, gas ratio and growth time on the quality of GNWs are systematically studied. The Raman spectrum shows that the obtained GNWs have a relatively high quality with a D to G peak ratio (ID/IG) of 0.42. Based on the optimization of the quality of GNWs, a field-effect transistor (FET) photodetector is prepared for the first time, and its photo-response mechanism is analyzed. The responsivity of the photodetector is 160 mA/W at 792 nm and 55 mA/W at 1550 nm. The results reveal that the GNWs are promising for high performance photodetectors.

Physical-layer authentication can address physical layer vulnerabilities and security threats in wireless sensor networks, and has been considered as an effective complementary enhancement to existing upper-layer authentication mechanisms. In this paper, to advance the existing research and improve the authentication performance, we propose a novel physical layer assisted authentication scheme for mobile wireless sensor networks. In our proposed scheme, we explore the reciprocity and spatial uncorrelation of the wireless channel to verify the identities of involved transmitting users and decide whether all data frames are from the same sender. In our proposed scheme, a new method is developed for the legitimate users to compare their received signal strength (RSS) records, which avoids the information from being disclosed to the adversary. Our proposed scheme can detect the spoofing attack even in a high dynamic environment. We evaluate our scheme through experiments under indoor and outdoor environments. Experiment results show that our proposed scheme is more efficient and achieves a higher detection rate as well as keeping a lower false alarm rate.

Graphene is an ideal material for wide spectrum detector owing to its special band structure, but its low light absorption and fast composite of photogenerated carriers lead to a weak response performance. In this paper, we designed a unique photoconductive graphene-InGaAs photodetector. The built-in electric field was formed between graphene and InGaAs, which can prolong the lifetime of photogenerated carriers and improve the response of devices by confining the holes. Compared with graphene-Si structure, a higher built-in electric field and reach to 0.54 eV is formed. It enables the device to achieve a responsivity of 60 AW−1 and a photoconductive gain of 79.4 at 792 nm. In the 1550 nm communication band, the responsivity of the device is also greater than 10 AW−1 and response speed is less than 2 ms. Meanwhile, the saturation phenomenon of light response was also found in this photoconductive graphene heterojunction detector during the experiment, we have explained the phenomenon by the capacitance theory of the built-in electric field, and the maximum optical responsivity of the detector is calculated theoretically, which is in good agreement with the measurement result.