High-quality surface-enhanced Raman scattering (SERS) spectra of aflatoxin (AF) B(1), B(2), G(1) and G(2) have been acquired using silver nanorod (AgNR) array substrates fabricated by oblique angle deposition method. Significant vibrational peaks are identified on the argon plasma-cleaned substrates, and those peaks agree very well with the Raman spectra calculated by density function theory (DFT). The concentration-dependent SERS detection is also explored. The relationship between the concentration (C) of different AFs and the SERS intensity (I) of the Raman peak at Δν = 1592 cm(-1) is found to follow the general relationship I = AC(α), with α ranging from 0.32 to 0.46 for the four AFs. The limits of detection (LODs) reach 5 × 10(-5) mol L(-1) for AFB(1), 1 × 10(-4) mol L(-1) for AFB(2), and 5 × 10(-6) mol L(-1) for both AFG(1) and AFG(2) in bulk solution, or 6.17 × 10(-16) mol/1.93 × 10(-4) ng of AFB(1), 1.23 × 10(-15) mol/3.88 × 10(-4) ng for AFB(2), 6.17 × 10(-17) mol/2.03 × 10(-5) ng for AFG(1), and 6.17 × 10(-17) mol/2.04 × 10(-5) ng for AFG(2) per laser spot. Principal component analysis (PCA) is used to successfully differentiate these four different kinds of AFs at different concentrations up to their detection limits. The LODs obtained from PCA agree with the LODs obtained by using peak fitting method. With such a low detection limit and outstanding differentiation ability, we prove the possibility of utilizing the SERS detection system as a platform for highly sensitive mycotoxin detection.

Organic materials with both high electron mobility and strong solid‐state emission are rare although for their importance to advanced organic optoelectronics. In this paper, triphenylethylenes with varying number of perylenediimide (PDI) unit (TriPE‐nPDIs, n = 1−3) are synthesized and their optical and charge‐transporting properties are systematically investigated. All the molecules exhibit strong solid‐stated near infrared (NIR) emission and some of them exhibit aggregation‐enhanced emission characteristics. Organic field‐effect transistors (OFETs) using TriPE‐nPDIs are fabricated. TriPE‐3PDI shows the best performance with maximum quantum yield of ≈30% and optimized electron mobility of over 0.01 cm2 V−1 s−1, which are the highest values among aggregation‐induced emission luminogens with NIR emissions reported so far. Photophysical property investigation and theoretical calculation indicate that the molecular conformation plays an important role on the optical properties of TriPE‐nPDI, while the result from film microstructure study reveals that the film crystallinity influences greatly their OFET device performance.

The single proton transfer at the different sites of the Watson-Crick (WC) guanine-cytosine (GC) DNA base pair are studied here using density functional methods. The conventional protonated structures, transition state (TS) and proton-transferred product (PT) structures of every relevant species are optimized. Each transition state and proton-transferred product structure has been compared with the corresponding conventional protonated structure to demonstrate the process of proton transfer and the change of geometrical structures. The relative energies of the protonated tautomers and the proton-transfer energy profiles in gas and solvent are analyzed. The proton-transferred product structure G(+H(+))-H(+)C(N3)(-H(+))(PT) has the lowest relative energy for which only two hydrogen bonds exist. Almost all 14 isomers of the protonated GC base pair involve hydrogen-bonded proton transfer following the three pathways, with the exception of structure G-H(+)C(O2). When the positive charge is primarily "located" on the guanine moiety (H(+)G-C, G-H(+)C(C4), and G-H(+)C(C6)), the H(1) proton transfers from the N(1) site of guanine to the N(3) site of cytosine. The structures G-H(+)C(C5) and G-H(+)C(C4) involve H(4a) proton transfer from the N(4) of cytosine to the O(6) site of guanine. H(2a) proton transfer from the N(2) site of guanine to the O(2) site of cytosine is found only for the structure G-H(+)C(C4). The structures to which a proton is added on the six-centered sites adjoining the hydrogen bonds are more prone to proton transfer in the gas phase, whereas a proton added on the minor groove and the sites adjoining the hydrogen bonds is favorable to the proton transfer in energy in the aqueous phase.

The neutral DNA trimers with the hydrogen atom added to the C8 site of the middle guanine-cytosine (GC) base pair, the DNA trimers protonated at the N7 site of the middle GC base pair, and the anionic species resulting from hydride addition to the C6 site of the middle GC base pair are investigated using theoretical methods. The canonical Watson-Crick structures (WC), transition state structures (TS) and proton-transferred structures (PT) of each relevant system are optimized in the gas phase and in aqueous solution, in order to understand the processes of proton transfer. The proton transfer reactions of the DNA trimers are compared with the corresponding isolated hydrogenated GC base pairs to explore the influence of the surrounding molecules and the base sequence. The proton transfer reactions of the neutral species, cations, and anions are compared, aiming to clarify the effects of the system's total charge. The results reveal that the surrounding molecules decrease the reaction energies of proton-transfer in aqueous solution. The structures with the dATGCAT and dGCGCGC sequences facilitate proton H4a transfer, but hinder proton H1 transfer. The structures with the dCGGCCG and dTAGCTA sequences facilitate proton H1 transfer. The net charge on the system plays an important role in determining the single and double proton-transfer patterns. Anions are more likely to experience proton-transfer reactions than neutral species and cations, and all the proton-transfer reactions of the anions are exothermic.