Structural Homogeneity of Macromolecular Networks by End-to-End Click Chemistry between Discrete Tetrahedral Star Macromolecules.

Cross-linking via the end-to-end click chemistry of multiarm star polymers creates polymer networks with minimal inhomogeneities. Although it has been suggested that the mechanical and swelling properties of such networks depend on the absence of defects, the structural details of homogeneous networks created by this method have not yet been studied at the molecular level. Here, we report the synthesis of discrete tetrahedral star macromolecules (dTSMs) composed of polylactide (PLA) arms with discrete molecular weight and sequence. Polymer networks prepared by 4 × 4 cross-linking by Cu-free strain-promoted cyclooctyne-azide click chemistry (SPAAC) reaction exhibited a high degree of swelling (>40 fold by weight) in solvents without sacrificing mechanical robustness (elastic modulus >4 kPa). The structural details of the networks were investigated by network disassembly spectrometry (NDS) using MALDI-TOF mass spectrometry. By implementing a cleavable repeating unit in the discrete PLA arms of dTSM in a sequence-specific manner, the networks could be disassembled into fragments having discrete molecular weights precisely representing their connectivity in the network. This NDS analysis confirmed that end-to-end click reactions of dTSM networks resulted in the formation of a homogeneous network above the critical concentration (∼10 w/v%) of building blocks in the solution.

Nondestructive Sequencing of Enantiopure Oligoesters by Nuclear Magnetic Resonance Spectroscopy.

Sequence-defined synthetic oligomers and polymers are promising molecular media for permanently storing digital information. However, the information decoding process relies on degradative sequencing methods such as mass spectrometry, which consumes the information-storing polymers upon decoding. Here, we demonstrate the nondestructive decoding of sequence-defined oligomers of enantiopure α-hydroxy acids, oligo(l-mandelic-co-d-phenyl lactic acid)s (oMPs), and oligo(l-lactic-co-glycolic acid)s (oLGs) by 13C nuclear magnetic resonance spectroscopy. We were able to nondestructively decode a bitmap image (192 bits) encoded using a library of 12 equimolar mixtures of an 8-bit-storing oMP and oLG, synthesized through semiautomated flow chemistry in less than 1% of the reaction time required for the repetition of conventional batch reactions. Our results highlight the potential of bundles of sequence-defined oligomers as efficient media for encoding and decoding large-scale information based on the automation of their synthesis and nondestructive sequencing processes.

Semiautomated synthesis of sequence-defined polymers for information storage.

Accelerated and parallel synthesis of sequence-defined polymers is an utmost challenge for realizing ultrahigh-density storage of digital information in molecular media. Here, we report step-economical synthesis of sequence-defined poly(l-lactic-co-glycolic acid)s (PLGAs) using continuous flow chemistry. A reactor performed the programmed coupling of the 2-bit storing building blocks to generate a library of their permutations in a single continuous flow, followed by their sequential convergences to a sequence-defined PLGA storing 64 bits in four successive flows. We demonstrate that a bitmap image (896 bits) can be encoded and decoded in 14 PLGAs using only a fraction of the time required for an equivalent synthesis by conventional batch processes. Accelerated synthesis of sequence-defined polymers could also contribute to macromolecular engineering with precision comparable to natural precedents.

Synthesis of Monolayer Gold Nanorings Sandwich Film and Its Higher Surface-Enhanced Raman Scattering Intensity.

Most previous studies relating to surface-enhanced Raman spectroscopy (SERS) signal enhancement were focused on the interaction between the light and the substrate in the x-y axis. 3D SERS substrates reported in the most of previous papers could contribute partial SERS enhancement via z axis, but the increases of the surface area were the main target for those reports. However, the z axis is also useful in achieving improved SERS intensity. In this work, hot spots along the z axis were specifically created in a sandwich nanofilm. Sandwich nanofilms were prepared with self-assembly and Langmuir-Blodgett techniques, and comprised of monolayer Au nanorings sandwiched between bottom Ag mirror and top Ag cover films. Monolayer Au nanorings were formed by self-assembly at the interface of water and hexane, followed by Langmuir-Blodgett transfer to a substrate with sputtered Ag mirror film. Their hollow property allows the light transmitted through a cover film. The use of a Ag cover layer of tens nanometers in thickness was critical, which allowed light access to the middle Au nanorings and the bottom Ag mirror, resulting in more plasmonic resonance and coupling along perpendicular interfaces (z-axis). The as-designed sandwich nanofilms could achieve an overall ~8 times SERS signals amplification compared to only the Au nanorings layer, which was principally attributed to enhanced electromagnetic fields along the created z-axis. Theoretical simulations based on finite-difference time-domain (FDTD) method showed consistent results with the experimental ones. This study points out a new direction to enhance the SERS intensity by involving more hot spots in z-axis in a designer nanostructure for high-performance molecular recognition and detection.

Synthesis of octahedral gold tip-blobbed nanoparticles and their dielectric sensing properties.

Site-selective synthesis of nanostructures is an important topic in the nanoscience community. Normally, the difference between seeds and deposition atoms in terms of crystallinity triggers the deposition atoms to grow initially at the specific site of nucleation. It is more challenging to control the deposition site of atoms that have the same composition as the seeds because the atoms tend to grow epitaxially, covering the whole surface of the seed nanoparticles. Gold (Au) nano-octahedrons used as seeds in this study possess obvious hierarchical surface energies depending on whether they are at vertices, edges, or terraces. Although vertices of Au nano-octahedrons have the highest surface energy, it remains a challenge to selectively deposit Au atoms at the vertices but not at the edges and faces; this selectivity is required to meet the ever-increasing demands of engineered nanomaterial properties. This work demonstrates an easy and robust method to precisely deposit Au nanoparticles at the vertices of Au nano-octahedrons via wet-chemical seed-mediated growth. The successful synthesis of octahedral Au tip-blobbed nanoparticles (Oh Au TBPs) benefited from the cooperative use of thin silver (Ag) layers at the surface of Au nano-octahedron seeds and iodide ions in the Au growth solution. As-synthesized Au nanostructures (i.e., Au TBPs) gave rise to hybrid optical properties, as evidenced from the UV-vis-NIR extinction spectra, in which a new extinction peak appeared after Au nanoparticles were formed at the vertices of Au nano-octahedrons. A sensitivity evaluation toward dielectric media of a mixture of dimethyl sulfoxide and water suggested that Au TBPs were more optically sensitive compared to the original Au nano-octahedrons. The method demonstrated in this work is promising in the synthesis of advanced Au nanostructures with hybrid optical properties for versatile applications, by engineering the surface energy of vertex-bearing Au nanostructures to trigger site-selective overgrowth of congener Au atoms.

Bimetallic junction mediated synthesis of multilayer graphene edges towards ultrahigh capacity for lithium ion batteries.

In this work, we report on a novel strategy to synthesize high-density graphene edges on a vertically-aligned nanorod array substrate based on multiple segmented Ni-Au units. The growth of graphene layers on Ni and Au was performed by chemical vapor deposition (CVD) leading to the effective generation of edge-rich multilayer graphene due to the distinct carbon solubility. The composite material was applied as an anode in a lithium ion battery (LIB) whose discharging capacity was found to closely depend on the total number of Ni-Au junctions within the vertical nanorods. Graphene deposited on the 19-junction composite Ni-(Au-Ni)9 exhibited an ultrahigh capacity of 86.3 µAh cm-2 at 50 µA cm-2 which was much higher than graphene deposited on 1-junction, 2-junction and pure Ni nanorods. This ultrahigh capacity was mainly ascribed to the generation of high-density graphene edges engineered by the bimetallic junction. The proposed strategy opens new appealing routes to synthesize high-density graphene edges using bimetallic junctions, which is promising for increasing the performance of LIBs and other electrochemical energy systems (supercapacitors, fuel cells, etc.).

Fourier Transform Surface Plasmon Resonance (FTSPR) with Gyromagnetic Plasmonic Nanorods.

An unprecedented active and dynamic sensing platform based on a LSPR configuration that is modulated by using an external magnetic field is reported. Electrochemically synthesized Au/Fe/Au nanorods exhibited plasmonically active behavior through plasmonic coupling, and the middle ferromagnetic Fe block responded to a magnetic impetus, allowing the nanorods to be modulated. The shear force variation induced by the specific binding events between antigens and antibodies on the nanorod surface is used to enhance the sensitivity of detection of antigens in the plasmonics-based sensor application. As a proof-of-concept, influenza A virus (HA1) was used as a target protein. The limit of detection was enhanced by two orders of magnitude compared to that of traditional LSPR sensing.

A close-packed 3D plasmonic superlattice of truncated octahedral gold nanoframes.

We report the surface-enhanced Raman scattering (SERS) enhancement of three-dimensional (3D) close-packed plasmonic superlattices of truncated octahedral gold nanostructures. Experimentally, we resolved two different types of hot spots, one originates from the face-to-face contacts and the other is from the edge-to-edge contacts among the 3D close-packed plasmonic superlattice of gold nanostructures. The high degree of homogeneity of truncated octahedral Au@Pt nanoparticles (TOh Au@Pt NPs) and truncated octahedral Pt@Au nanoframes (TOh Pt@Au NFs) allowed them to self-assemble into remarkable 3D close-packed plasmonic superlattices. The morphological evolution and the corresponding optical behavior of TOh Pt@Au NFs were systematically monitored during each synthetic process. The measured SERS enhancement on the hot spots from the edge-to-edge contacts of TOh Pt@Au NFs was five times greater than the SERS response from the analogous face-to-face contacts of TOh Au@Pt NPs under the same given experimental conditions. The hollow interior and well-defined structural morphology of TOh Pt@Au NFs will allow researchers to design highly programmable 3D plasmonic superlattices for efficient SERS enhancement.

Interfacial double layer mediated electrochemical growth of thin-walled platinum nanotubes.

This work demonstrates that thin-walled platinum nanotubes can be readily synthesized by controlling the interfacial double layer in alumina nanochannels. The gradient distribution of ions in nanochannels enables the creation of Pt nanotubes with walls as thin as 5 nm at the top end when using a solution containing polyvinylpyrrolidone (PVP) and chloroplatinic acid (H2PtCl6) under the influence of an electric potential in nanochannels. The highly efficient formation of thin-walled Pt nanotubes is a result of the concentration gradient of [Formula: see text] and a thick double layer, which was caused by the low concentration of Pt precursors and the enhanced surface charge density induced by protonated PVP steric adsorption. This well-controlled synthesis reveals that the interfacial double layer is a useful tool to tailor the structure of nanomaterials in a nanoscale space, and holds promise in the construction of more complex functional nanostructures.

Component conversion from pure Au nanorods to multiblock Ag-Au-Ag nanorods assisted by Pt nanoframe templates.

We developed a new method for synthesizing multiblock Ag-Au-Ag nanorods using Pt nanoframes that had been deposited on the edges of Au nanorod seeds. As a function of Au etching time, the length of the Au nanorod decreased symmetrically starting from the two ends, leading to the formation of empty inner space at the ends. Subsequent reduction of Ag ions could be selectively performed in the inner space confined by Pt nanoframes and the resulting Ag-Au-Ag nanorods exhibited characteristic LSPR modes originating from each block component (in a transverse direction) and SPR coupling (in a longitudinal direction). The high quality of the resulting multiblock nanorods enabled observation of the longitudinal quadrupole mode that was induced by Ag-Au SPR coupling in a long axis. The mode exhibited high sensitivity in accordance with the change in the surrounding media, demonstrating great potential for sensor applications.

Synthesis and optical property characterization of elongated AuPt and Pt@Au metal nanoframes.

We report a facile method to synthesize elongated nanoframes consisting of Pt and Au in solution. Pentagonal Au nanorods served as templates and successfully led to an elongated AuPt nanoframe after etching the core Au. Subsequently, the coating of Au around Pt ridges resulted in Pt@Au metal nanoframes. The resulting elongated nanostructure exhibited 5 well-defined ridges continuously connected along the long axis. During the shape evolution from pure Au nanorods to elongated Pt@Au metal nanoframes, their corresponding localized surface plasmon resonance bands were monitored. Especially, unique surface plasmon features were observed for elongated Pt@Au nanoframes where the short-axis oscillation of surface free electrons is strongly coupled but the long-axis oscillation is not coupled among the ridges.

Octahedral and Cubic Gold Nanoframes with Platinum Framework.

Herein, we report a general synthetic pathway to various shapes of three-dimensional (3D) gold nanoframes (NFs) embedded with a Pt skeleton for structural rigidity. The synthetic route comprises three steps: site-specific (edge and vertex) deposition of Pt, etching of inner Au, and regrowth of Au on the Pt framework. Site-specific reduction of Pt on Au nanoparticles (NPs) led to the high-quality of 3D Au NFs with good structural rigidity, which allowed the detailed characterization of the corresponding 3D metal NFs. The synthetic method described here will open new avenues toward many new kinds of 3D metal NFs.

Fabrication of shape-controlled reduced graphene oxide nanorings by Au@Pt nanoring lithography.

We fabricated a variety of reduced graphene oxide (RGO) nanoring arrays using Au@Pt nanoplates as a pattern mask. RGO nanoflakes were assembled into a 2-dimensional assembly at the water-oil interface, and then various shapes of Au@Pt nanoplates were utilized as a pattern mask in order to convert the RGO into circular, triangular, and hexagonal RGO nanorings.

Fabrication of 2D Au nanorings with Pt framework.

Surface plasmonics of nanomaterials has been one of the main research themes in nanoscience. Spherical and elongated nanoparticles show their corresponding unique optical features mainly depending on the physical dimensions. Here we successfully synthesized Au nanorings having Pt framework (Pt@Au nanorings) with high uniformity through wet-chemistry. The synthetic strategy consisted of serial reactions involving site-selective growth of Pt on the rim of Au nanoplates, subsequent etching of Au nanoplates, followed by regrowth of Au on the Pt rim. In this synthetic method, Au(3+) ions exhibited dual functionality as an etchant and a metal precursor. The resultant product, Pt@Au nanorings, exhibited unique localized surface plasmon resonance (LSPR) bands originating from the Au shell. The inner Pt skeleton turns out to be important to hold structural stability.

Site-specific growth of a Pt shell on Au nanoplates: tailoring their surface plasmonic behavior.

In this report, we tune the surface plasmonic behavior of Au nanoplates depending on the morphology of the Pt shell in which Pt is considered as a less optically inactive element. We describe the synthesis of flat Au nanoplates coated with Pt via rim-preferential or uniform growth methods. Depending on the site-selective growth of Pt on core Au nanoplates, the aspect ratio of the resulting Au@Pt nanoplates was tunable and their corresponding surface plasmon resonance (SPR) bands were controlled accordingly. Although Pt is regarded as an optically weak component in visible and near infrared spectral windows, a Pt coating affects the SPR behavior of core Au nanoplates due to effective surface plasmon (SP) coupling between the Au core and the deposited Pt shell. We systematically investigated the optical properties of uniformly grown (Au@Pt(uni)) and rim-preferentially grown (Au@Pt(rim)) Au@Pt nanoplates by observing their SPR band shifts compared to SPR of Au nanoplates. Due to the structural rigidity conferred by the Pt coating, the Au@Pt nanoplates can be easily transferred to the investigated solvents.

Influence of iodide ions on morphology of silver growth on gold hexagonal nanoplates.

Different morphologies of Au@Ag nanocrystals have been successfully synthesized using iodide ions in growth solutions consisting of ascorbic acid, NaOH, and CTAB. Without I(-) ions in growth solution, there were unnoticeable changes in morphology. On the other hand, with addition of I(-) ions, remarkable changes were observed including formation of hexagonal bipyramidal nanocrystals. Ag(+) ions were reduced and deposited on {111} facets of gold hexagonal nanoplates (GHNs), and hexagonal bipyramidal nanoparticles were formed more quickly in the presence of I(-) ions than without I(-) ions. Our studies reveal that I(-) ion affects the selective growth of Ag onto GHNs. This can be explained by the decrease in the surface redox potential of nanocrystals that occurs by combining with the AgI complex on the metallic surface. These results were confirmed by FESEM images, UV-vis-NIR spectra, and TEM images.

A virtual reality application in role-plays of social skills training for schizophrenia: a randomized, controlled trial.

Although social skills training (SST) is an effective approach for improving social skills for schizophrenia, the motivational deficit attenuates its efficacy. Virtual reality (VR) applications have allowed individuals with mental disabilities to enhance their motivation for rehabilitation. We compared SST using VR role-playing (SST-VR) to SST using traditional role-playing (SST-TR). This randomized, controlled trial included 91 inpatients with schizophrenia who were assigned to either SST-VR (n=46) or SST-TR (n=45). Both groups were administered over 10 semiweekly group sessions. An experienced, blinded rater assessed vocal, nonverbal and conversational skills. We also obtained data on motivation for SST and various social abilities. Throughout the 10 sessions, the SST-VR group (n=33) showed greater interest in SST and generalization of the skills than the SST-TR group (n=31). After SST, the SST-VR group improved more in conversational skills and assertiveness than the SST-TR group, but less in nonverbal skills. The VR application in role-plays of SST for schizophrenia may be particularly beneficial in terms of improving the conversational skills and assertiveness, possibly through its advantages in enhancing motivation for SST and generalization of the skills, and thus it may be a useful supplement to traditional SST.

Combinatorial expression of bacterial whole mevalonate pathway for the production of beta-carotene in E. coli.

The increased synthesis of building blocks of IPP (isopentenyl diphosphate) and DMAPP (dimethylallyl diphosphate) through metabolic engineering is a way to enhance the production of carotenoids. Using E. coli as a host, IPP and DMAPP supply can be increased significantly through the introduction of foreign MVA (mevalonate) pathway into it. The MVA pathway is split into two parts with the top and bottom portions supplying mevalonate from acetyl-CoA, and IPP and DMAPP from mevalonate, respectively. The bottom portions of MVA pathway from Streptococcus pneumonia, Enterococcus faecalis, Staphylococcus aureus, Streptococcus pyogenes and Saccharomyces cerevisiae were compared with exogenous mevalonate supplementation for beta-carotene production in recombinant Escherichia coli harboring beta-carotene synthesis genes. The E. coli harboring the bottom MVA pathway of S. pneumoniae produced the highest amount of beta-carotene. The top portions of MVA pathway were also compared and the top MVA pathway of E. faecalis was found out to be the most efficient for mevalonate production in E. coli. The whole MVA pathway was constructed by combining the bottom and top portions of MVA pathway of S. pneumoniae and E. faecalis, respectively. The recombinant E. coli harboring the whole MVA pathway and beta-carotene synthesis genes produced high amount of beta-carotene even without exogenous mevalonate supplementation. When comparing various E. coli strains - MG1655, DH5alpha, S17-1, XL1-Blue and BL21 - the DH5alpha was found to be the best beta-carotene producer. Using glycerol as the carbon source for beta-carotene production was found to be superior to glucose, galactose, xylose and maltose. The recombinant E. coli DH5alpha harboring the whole MVA pathway and beta-carotene synthesis genes produced beta-carotene of 465mg/L at glycerol concentration of 2% (w/v).

Micronucleus Test of Polycan™, ß-Glucan Originated from Aureobasidium, in Bone Marrow Cells of Male ICR Mice.

In this research the genotoxic effect of Polycan™ ß-glucans originated from Aureobasidium pullulans SM-2001, was evaluated using the mouse micronucleus test. Polycan™ was administered once a day for 2 days by oral gavage to male ICR mice at doses of 1000, 500 and 250 mg/kg. Cyclophosphamide was used as a known genotoxic agent in a positive control group. The appearance of a micronucleus is used as an index for genotoxic potential. The results obtained indicated that Polycan™ shows no genotoxicity effect up to 1000 mg/kg dosing levels. In addition, it is also considered that there were no problems from cytotoxicity of Polycan™ tested in this study because the polychromatic erythrocyte ratio was detected as > 0.47 in all tested groups.

Effects of beta-glucan from Aureobasidium pullulans on acute inflammation in mice.

The effects of beta-glucan isolated from Aureobasidium pullulans were observed on acute xylene-induced inflammation. beta-glucan at a dose of 62.5, 125 or 250 mg/kg were administered once orally to xylene-treated mice (0.03 mL of xylene was applied on the anterior surface of the right ear to induce inflammation), and the body weight change, ear weight, histological profiles and histomorphometrical analyses of ear were conducted upon sacrifice. The xylene was topically applied 30 min after dosing with beta-glucan. The results were compared to those of diclofenac, indomethacin and dexamethasone (15 mg/kg injected once intraperitoneally). All animals were sacrificed 2 h after xylene application. Xylene application resulted in marked increases in induced ear weights compared to that of intact control ear; hence, the differences between intact and induced ear were also significantly increased. The histological characteristics of acute inflammation, such as severe vasodilation, edematous changes of skin and infiltration of inflammatory cells, were detected in xylene-treated control ears with marked increase in the thickness of the ear tissues. However, these xylene-induced acute inflammatory changes were significantly and dose-dependently decreased by beta-glucan treatment. We conclude that beta-glucan from A. pullulans has a somewhat favorable effect in the reduction of the acute inflammatory responses induced by xylene application in mice.