Novel Molecular Organic Framework Composite Molecularly Imprinted Nanofibrous Membranes with a Bioinspired Viscid Bead Structure for Selective Recognition and Separation of Atrazine.

In this work, novel atrazine (ATZ) molecularly imprinted nanofibrous membranes (A-MNMs) with a molecular organic framework (MOF)-based viscid bead structure were developed based on a natural spider-web-inspired strategy for selective separation of ATZ. Poly(vinylidene fluoride)/poly(vinyl alcohol) (PVDF/PVA) blended nanofibrous membranes as the basal membrane were synthesized by electrospinning technology combined with a chemical cross-linking procedure. The most critical design is that MOF nanocrystals as the matrix of the viscid bead structure were assembled on the PVDF/PVA blended nanofibrous membrane surface and the specific recognition sites were efficiently constructed on the surface and pores of the MOF-based viscid bead structure by a surface imprinting strategy. Significantly, the as-synthesized MOF-based viscid bead structure has an enhanced specific surface area, which helps to form abundant specific recognition sites in A-MNMs. Therefore, the A-MNMs with a spider-web-like structure presented an enhanced rebinding capacity (37.62 mg g-1) and permselectivity (permselectivity factors ß were 4.21 and 4.31) toward ATZ. Moreover, the A-MNMs display strong practicability in separation of ATZ from simulated environmental water samples. The presented work has shown tremendous potential for preparing natural spider-web-like molecularly imprinted membranes (MIMs) for selective separation of environment pollutants.

Multifunctional-imprinted nanocomposite membranes with thermo-responsive biocompatibility for selective/controllable recognition and separation application.

Inspired by the biomimetic modification strategy of dopamine self-polymerization technique, molecularly imprinted nanocomposite membranes (MINCMs) with thermo-responsive rebinding and separation performance were synthesized and evaluated. Herein, the Au/SiO2-based multilevel structure had been successfully obtained onto the polydopamine (pDA) modified membrane surfaces. Afterward, the poly(N-isopropylacrylamide)-based biomolecule-imprinted sites were adequately constructed by developing a photoinitiated atom transfer radical polymerization (pATRP) imprinting strategy using the high-biocompatible ovalbumin (Ova, pI 4.6) as template molecule. Therefore, thermo-responsive 'specific recognition sites' toward Ova were then achieved on the as-prepared MINCMs after the well-designed imprinting process. When the external temperature was set at 37 °C, excellent ovalbumin rebinding capacity (33.26 mg/g), selectivity factor (3.06) and structural stability were obtained. Importantly, as to the controllable biocompatibility research of this work, the bare glass and Ova-bound-MINCMs (the MINCMs were bound with Ova) showed basically the same cell adhesion behaviors and viability, indicating the excellent biocompatibility of the Ova-bound-MINCMs. Additionally, efficient and rapid regulation of cell adhesion/detachment on ovalbumin-bound MINCMs could be still obtained even after 10 cycles of temperature-switch process, which indicated that the as-prepared MINCMs had strong ability to work under high intensity and long continuous operation.

Three-dimensional macroporous wood-based selective separation membranes decorated with well-designed Nd(III)-imprinted domains: A high-efficiency recovery system for rare earth element.

Three-dimensional (3D) basswood materials, for the first time, were successfully used for the construction of rare-earth Nd(III)-imprinted nanocomposite membranes. Herein, polydopamine (PDA)-modified layers could be initially synthesized on basswood surfaces. After the double-bonded modification procedure, the 3D wood-based ionic imprinted membranes (3DW-IIMs) system was finally accomplished by developing a re-modified two-step-temperature free radical polymerization process. The as-design PDA@basswood surface structure was first proposed and applied as imprinting-initiated factors for the preparation of Nd(III)-imprinted sites. Importantly, excellent rebinding capacity (120.87 mg g-1), adsorption kinetics and permselectivity coefficients (more than 10) were achieved successfully. Furthermore, an important research result had also been found that the PDA-modified layers caused significant promotions to the rebinding capacities of the as-prepared 3DW-IIMs, that is to say, more and more Nd(III)-imprinted sites could be synthesized because of the PDA-modified surfaces. The as-obtained selective rebinding and separation results together with the green natural wood-based materials strongly demonstrated that our synthesis methodology of 3DW-IIMs had great potential for applications in various fields of rare earth separation, chemical industry, and environment protection.

Multilevel mineral-coated imprinted nanocomposite membranes for template-dependent recognition and separation: A well-designed strategy with PDA/CaCO3-based loading structure.

In spite of the intense efforts in selective separation field, the utilization and preparation of membrane-associated molecularly imprinted membranes with both enhanced rebinding capacities and high permselectivity performance still remain strong challenges. Herein, the bioinspired PDA-modified porous regenerated cellulose membrane (pRCMs) with mineral-coated multilevel structure was first proposed for the preparation of PDA/CaCO3-based imprinted nanocomposite membranes (PCIMs), m-cresol was chosen as the template molecule. Importantly, this bioinspired methodology was redeveloped and optimized to obtain abundant and uniformly distributed CaCO3 nanocomposite on the surfaces of PDA@pRCMs. The as-designed sandwich-like imprinting structure were then constructed on PDA/CaCO3-based surfaces by developing a simple sol-gel imprinting process. Attributing to the design of the uniform CaCO3/PDA@pRCMs surfaces, amount of m-cresol-imprinted sites and permeation selectivity could be both optimized, it was no surprise that more excellent rebinding capacity (97.4 mg g-1), fast adsorption kinetics and high permselectivity coefficients (more than 13) were successfully achieved. Importantly, the whole synthesis process was conducted without complicated procedures and polluting the environment. Finally, the experimental results mentioned above, together with the green synthesis processes strongly demonstrated that our synthesis methodology of PCIMs had great potential for applications in various fields of selective separation, chemical industry, environment, biological medicine and so on.

Bio-inspired fabrication of Ester-functionalized imprinted composite membrane for rapid and high-efficient recovery of lithium ion from seawater.

Lithium ion (Li+) is one of the important sustainable resource and it's urgently demanded to develop high-selectivity and high-efficient method to extract of Li+ from seawater. Hence, we propose the ester-functionalized ion-imprinted membrane (IIMs) with high selectivity and stability for the rebinding and separation of Li+ in aqueous medium via ion imprinted technology and membrane separation technology. In this work, the hydrophilic polydimethylsiloxane membranes (PDMS) are synthesized by self-polymerization of dopamine (DA) in aqueous solution, resulting in the fabrication of dense poly-dopamine (PDA) layer on the surface of PDMS (PDMS-PDA). In view of weak bonding forces (such as hydrogen bond, ionic bond and Van der Waals' force) between traditional imprinted polymer and ligand, the ester groups are formed between modified PDMS-PDA and ligand by surface grafting. The obtained Li+ imprinted membranes (Li-IIMs) have a suitable cavity and high adsorption capacity toward Li+ which reveal a high rebinding capacity (50.872 mg g-1) toward Li+ based on ample rebinding sites and strong affinity force. The superior relative selectivity coefficients (αNa/Li, αK/Li and αRb/Li are 1.71, 4.56 and 3.80, respectively) can be also achieved. The selectivity factors of Li-IIMs for Na+, K+ and Rb+ are estimated to be 2.52, 2.8 and 3.03 times larger than Li+ non-imprinted membranes (Li-NIMs), which imply the superior selectivity of Li-IIMs toward Li+. The regeneration ability of Li-IIMs is observed by systematic batch experiments. In summary, it can be concluded that the rebinding capacities of Li-IIMs is slightly decrease after eluting process, owing to the Li-IIMs with outstanding stability performance. Presentation of the method pave a fine prospect for coming true the long-term use of imprinted membrane.

A lithographically patterned capacitor with horizontal nanowires of length 2.5 mm.

A symmetrical hybrid capacitor consisting of interdigitated, horizontal nanowires is described. Each of the 750 nanowires within the capacitor is 2.5 mm in length, consisting of a gold nanowire core (40 × ≈200 nm) encapsulated within a hemicylindrical shell of δ-phase MnO2 (thickness = 60-220 nm). These Au@δ-MnO2 nanowires are patterned onto a planar glass surface using lithographically patterned nanowire electrodeposition (LPNE). A power density of 165 kW/kg and energy density of 24 Wh/kg were obtained for a typical nanowire array in which the MnO2 shell thickness was 68 ± 8 nm. Capacitors incorporating these ultralong nanowires lost ≈10% of their capacity rapidly, during the first 20 discharge cycles, and then retained 90% of their maximum capacity for the ensuing 6000 cycles. The ability of capacitors consisting of ultralong Au@δ-MnO2 nanowires to simultaneously deliver high power and high capacity with acceptable cycle life is demonstrated.

Electroluminescent, polycrystalline cadmium selenide nanowire arrays.

Electroluminescence (EL) from nanocrystalline CdSe (nc-CdSe) nanowire arrays is reported. The n-type, nc-CdSe nanowires, 400-450 nm in width and 60 nm in thickness, were synthesized using lithographically patterned nanowire electrodeposition, and metal-semiconductor-metal (M-S-M) devices were prepared by the evaporation of two gold contacts spaced by either 0.6 or 5 µm. These M-S-M devices showed symmetrical current voltage curves characterized by currents that increased exponentially with applied voltage bias. As the applied biased was increased, an increasing number of nanowires within the array "turned on", culminating in EL emission from 30 to 50% of these nanowires at applied voltages of 25-30 V. The spectrum of the emitted light was broad and centered at 770 nm, close to the 1.74 eV (712 nm) band gap of CdSe. EL light emission occurred with an external quantum efficiency of 4 × 10(-6) for devices with a 0.60 µm gap between the gold contacts and 0.5 × 10(-6) for a 5 µm gap-values similar to those reported for M-S-M devices constructed from single-crystalline CdSe nanowires. Kelvin probe force microscopy of 5 µm nc-CdSe nanowire arrays showed pronounced electric fields at the gold electrical contacts, coinciding with the location of strongest EL light emission in these devices. This electric field is implicated in the Poole-Frenkel minority carrier emission and recombination mechanism proposed to account for EL light emission in most of the devices that were investigated.

Laser annealing of nanocrystalline gold nanowires.

The efficacy of laser annealing for the thermal annealing of nanocrystalline gold nanowires is evaluated. Continuous laser illumination at 532 nm, focused to a 0.5 µm diameter spot, was rastered perpendicular to the axis of nanocrystalline gold nanowire at ∼2 kHz. This rastered beam was then scanned down the nanowire at velocities from 7 to 112 nm/s. The influence on the electrical resistance of the gold nanowire of laser power, polarization, translation speed, and nanowire width were evaluated. Nanocrystalline gold nanowires were prepared on glass surfaces using the lithographically patterned nanowire electrodeposition (LPNE) method. These nanowires had a rectangular cross section with a height of 20 (± 3) nm and widths ranging from 76 to 274 nm. The 4-contact electrical resistance of the nanowire is measured in situ during laser annealing and a real-time decrease in electrical resistance of between 30 and 65% is observed, depending upon the laser power and scan rate along the nanowire. These resistance decreases are associated with an increase in the mean grain diameter within these nanowires, measured using transmission electron microscopy, of up to 300%. The observed decrease in the electrical resistance induced by laser annealing conforms to classical predictions based upon the reduction in grain boundary scattering induced by grain growth.

Field-effect transistors from lithographically patterned cadmium selenide nanowire arrays.

Field-effect transistors (NWFETs) have been prepared from arrays of polycrystalline cadmium selenide (pc-CdSe) nanowires using a back gate configuration. pc-CdSe nanowires were fabricated using the lithographically patterned nanowire electrodeposition (LPNE) process on SiO(2)/Si substrates. After electrodeposition, pc-CdSe nanowires were thermally annealed at 300 °C × 4 h either with or without exposure to CdCl(2) in methanol-a grain growth promoter. The influence of CdCl(2) treatment was to increase the mean grain diameter from 10 to 80 nm as determined by grazing incidence X-ray diffraction and to convert the crystal structure from cubic to wurtzite. Measured transfer characteristics showed an increase of the field effect mobility (µ(eff)) by an order of magnitude from 1.94 × 10(-4) cm(2)/(V s) to 23.4 × 10(-4) cm(2)/(V s) for pc-CdSe nanowires subjected to the CdCl(2) treatment. The CdCl(2) treatment also reduced the threshold voltage (from 20 to 5 V) and the subthreshold slope (by ~35%). Transfer characteristics for pc-CdSe NWFETs were also influenced by the channel length, L. For CdCl(2)-treated nanowires, µ(eff) was reduced by a factor of eight as L increased from 5 to 25 µm. These channel length effects are attributed to the presence of defects including breaks and constrictions within individual pc-CdSe nanowires.

High-throughput fabrication of photoconductors with high detectivity, photosensitivity, and bandwidth.

Nanocrystalline cadmium selenide (nc-CdSe) was electrodeposited within a sub-50 nm gold nanogap, prepared by feedback-controlled electromigration, to form a photoconductive metal-semiconductor-metal nanojunction. Both gap formation and electrodeposition were rapid and automated. The electrodeposited nc-CdSe was stoichiometric, single cubic phase with a mean grain diameter of ∼7 nm. Optical absorption, photoluminescence, and the spectral photoconductivity response of the nc-CdSe were all dominated by band-edge transitions. The photoconductivity of these nc-CdSe-filled gold nanogaps was characterized by a detectivity of 6.9 × 10(10) Jones and a photosensitivity of 500. These devices also demonstrated a maximum photoconductive gain of ∼45 and response and recovery times below 2 µs, corresponding to a 3 dB bandwidth of at least 175 kHz.

A chemically-responsive nanojunction within a silver nanowire.

The formation of a nanometer-scale chemically responsive junction (CRJ) within a silver nanowire is described. A silver nanowire was first prepared on glass using the lithographically patterned nanowire electrodeposition method. A 1-5 nm gap was formed in this wire by electromigration. Finally, this gap was reconnected by applying a voltage ramp to the nanowire resulting in the formation of a resistive, ohmic CRJ. Exposure of this CRJ-containing nanowire to ammonia (NH(3)) induced a rapid (<30 s) and reversible resistance change that was as large as ΔR/R(0) = (+)138% in 7% NH(3) and observable down to 500 ppm NH(3). Exposure to water vapor produced a weaker resistance increase of ΔR/R(0,H(2)O) = (+)10-15% (for 2.3% water) while nitrogen dioxide (NO(2)) exposure induced a stronger concentration-normalized resistance decrease of ΔR/R(0,NO(2)) = (-)10-15% (for 500 ppm NO(2)). The proposed mechanism of the resistance response for a CRJ, supported by temperature-dependent measurements of the conductivity for CRJs and density functional theory calculations, is that semiconducting p-type Ag(x)O is formed within the CRJ and the binding of molecules to this Ag(x)O modulates its electrical resistance.

Mesoporous manganese oxide nanowires for high-capacity, high-rate, hybrid electrical energy storage.

Arrays of mesoporous manganese dioxide, mp-MnO(2), nanowires were electrodeposited on glass and silicon surfaces using the lithographically patterned nanowire electrodeposition (LPNE) method. The electrodeposition procedure involved the application, in a Mn(ClO(4))(2)-containing aqueous electrolyte, of a sequence of 0.60 V (vs MSE) voltage pulses delineated by 25 s rest intervals. This "multipulse" deposition program produced mp-MnO(2) nanowires with a total porosity of 43-56%. Transmission electron microscopy revealed the presence within these nanowires of a network of 3-5 nm diameter fibrils that were X-ray and electron amorphous, consistent with the measured porosity values. mp-MnO(2) nanowires were rectangular in cross-section with adjustable height, ranging from 21 to 63 nm, and adjustable width ranging from 200 to 600 nm. Arrays of 20 nm × 400 nm mp-MnO(2) nanowires were characterized by a specific capacitance, C(sp), of 923 ± 24 F/g at 5 mV/s and 484 ± 15 F/g at 100 mV/s. These C(sp) values reflected true hybrid electrical energy storage with significant contributions from double-layer capacitance and noninsertion pseudocapacitance (38% for 20 nm × 400 nm nanowires at 5 mV/s) coupled with a Faradaic insertion capacity (62%). These two contributions to the total C(sp) were deconvoluted as a function of the potential scan rate.

Tunable photoconduction sensitivity and bandwidth for lithographically patterned nanocrystalline cadmium selenide nanowires.

Nanocrystalline cadmium selenide (nc-CdSe) nanowires were prepared using the lithographically patterned nanowire electrodeposition method. Arrays of 350 linear nc-CdSe nanowires with lateral dimensions of 60 nm (h) × 200 nm (w) were patterned at 5 µm pitch on glass. nc-CdSe nanowires electrodeposited from aqueous solutions at 25 °C had a mean grain diameter, d(ave), of 5 nm. A combination of three methods was used to increase d(ave) to 10, 20, and 100 nm: (1) The deposition bath was heated to 75 °C, (2) nanowires were thermally annealed at 300 °C, and (3) nanowires were exposed to methanolic CdCl(2) followed by thermal annealing at 300 °C. The morphology, chemical composition, grain diameter, and photoconductivity of the resulting nanowires were studied as a function of d(ave). As d(ave) was increased from 10 to 100 nm, the photoconductivity response of the nanowires was modified in two ways: First, the measured photoconductive gain, G, was elevated from G = 0.017 (d(ave) = 5 nm) to ∼4.9 (100 nm), a factor of 290. Second, the photocurrent rise time was increased from 8 µs for d(ave) = 10 nm to 8 s for 100 nm, corresponding to a decrease by a factor of 1 million of the photoconduction bandwidth from 44 kHz to 44 mHz.

Remote multi-color excitation using femtosecond propagating surface plasmon polaritons in gold films.

We demonstrate dual-color nonlinear excitation of quantum dots positioned onto a gold film at distances up to 40 µm away from a micrometer sized focused laser spot. We attribute the observed remote nonlinear signal to the excitation of two independent surface plasmon polariton (SPP) modes excited at the laser spot in the gold film, which subsequently propagate in a collinear fashion to a distant site and provide the surface field required for nonlinear excitation of the target. This scheme decouples the illuminating photon flux from surface plasmon mediated nonlinear excitation of the target, which provides more control of unwanted heating effects at the target site and represents an attractive approach for surface-mediated femtosecond nonlinear examinations of molecules.