Ultralow flexural properties of copper microhelices fabricated via electrodeposition-based three-dimensional direct-writing technology.

Helical metallic micro/nanostructures as functional components have considerable potential for future miniaturized devices, based on their unique mechanical and electrical properties. Thus, understanding and controlling the mechanical properties of metallic helices is desirable for their practical application. Herein, we implemented a direct-writing technique based on the electrodeposition method to grow copper microhelices with well-defined and programmable three-dimensional (3D) features. The mechanical properties of the 3D helical structures were studied by the electrically induced quasistatic and dynamic electromechanical resonance technique. These methods mainly explored the static pull-in process and the dynamic electromechanical response, respectively. It was found that the center-symmetric and vertical double copper microhelix structure with 1.2 µm wire diameter has a flexural rigidity of 0.9 × 10-14 N m2 and the single vertical copper microhelix structure with 1.1 µm wire diameter has a flexural rigidity of 0.5989 × 10-14 N m2. By comparing with microwires and other reported micro/nanohelices, we found that the copper microhelices reported here had an ultralow stiffness (about 0.13 ± 0.01 N m-1). It is found that the experimental results agree well with the finite element calculations. The proposed method can be used to fabricate and measure the flexural properties of three-dimensional complex micro/nanowire structures, and may have a profound effect on the application of microhelices in various useful microdevices such as helix-based microelectromechanical switches, sensors and actuators based on their unique mechanical properties.

Phytotoxicity of 4,8-dihydroxy-1-tetralone isolated from Carya cathayensis Sarg. to various plant species.

The aqueous extract from Carya cathayensis Sarg. exocarp was centrifuged, filtered, and separated into 11 elution fractions by X-5 macroporous resin chromatography. A phenolic compound, 4,8-dihydroxy-1-tetralone (4,8-DHT) was isolated from the fractions with the strongest phytotoxicity by bioassy-guided fractionation, and investigated for phytotoxicity on lettuce (Latuca sativa L.), radish (Raphanus sativus L.), cucumber (Cucumis sativus L.), onion (Allium cepa L.) and wheat (Triticum aestivum L.). The testing results showed that the treatment with 0.6 mM 4,8-DHT could significantly depress the germination vigor of lettuce and wheat, reduce the germination rate of lettuce and cucumber, and also inhibit radicle length, plumule length, and fresh weight of seedlings of lettuce and onion, but could significantly promote plumule length and fresh weight of seedlings of cucumber (p < 0.05). For the tested five plants, the 4,8-DHT was the most active to the seed germination and seedling growth of lettuce, indicating that the phytotoxicity of 4,8-DHT had the selectivity of dosage, action target (plant type) and content (seed germination or seedling growth).

Improved atomic force microscope infrared spectroscopy for rapid nanometer-scale chemical identification.

Atomic force microscope infrared spectroscopy (AFM-IR) can perform IR spectroscopic chemical identification with sub-100 nm spatial resolution, but is relatively slow due to its low signal-to-noise ratio (SNR). In AFM-IR, tunable IR laser light is incident upon a sample, which results in a rise in temperature and thermomechanical expansion of the sample. An AFM tip in contact with the sample senses this nanometer-scale photothermal expansion. The tip motion induces cantilever vibrations, which are measured either in terms of the peak-to-peak amplitude of time-domain data or the integrated magnitude of frequency-domain data. Using a continuous Morlet wavelet transform to the cantilever dynamic response, we show that the cantilever dynamics during AFM-IR vary as a function of both time and frequency. Based on the observed cantilever response, we tailor a time-frequency-domain filter to identify the region of highest vibrational energy. This approach can increase the SNR of the AFM cantilever signal, such that the throughput is increased 32-fold compared to state-of-the art procedures. We further demonstrate significant increases in AFM-IR imaging speed and chemical identification of nanometer-scale domains in polymer films.

Modeling and measurement of geometrically nonlinear damping in a microcantilever-nanotube system.

Nonlinear mechanical systems promise broadband resonance and instantaneous hysteretic switching that can be used for high sensitivity sensing. However, to introduce nonlinear resonances in widely used microcantilever systems, such as AFM probes, requires driving the cantilever to an amplitude that is too large for any practical applications. We introduce a novel design for a microcantilever with a strong nonlinearity at small cantilever oscillation amplitude arising from the geometrical integration of a single BN nanotube. The dynamics of the system was modeled theoretically and confirmed experimentally. The system, besides providing a practical design of a nonlinear microcantilever-based probe, demonstrates also an effective method of studying the nonlinear damping properties of the attached nanotube. Beyond the typical linear mechanical damping, the nonlinear damping contribution from the attached nanotube was found to be essential for understanding the dynamical behavior of the designed system. Experimental results obtained through laser microvibrometry validated the developed model incorporating the nonlinear damping contribution.

Atomic force microscope infrared spectroscopy on 15 nm scale polymer nanostructures.

We measure the infrared spectra of polyethylene nanostructures of height 15 nm using atomic force microscope infrared spectroscopy (AFM-IR), which is about an order of magnitude improvement over state of the art. In AFM-IR, infrared light incident upon a sample induces photothermal expansion, which is measured by an AFM tip. The thermomechanical response of the sample-tip-cantilever system results in cantilever vibrations that vary in time and frequency. A time-frequency domain analysis of the cantilever vibration signal reveals how sample thermomechanical response and cantilever dynamics affect the AFM-IR signal. By appropriately filtering the cantilever vibration signal in both the time domain and the frequency domain, it is possible to measure infrared absorption spectra on polyethylene nanostructures as small as 15 nm.

Intrinsically high-Q dynamic AFM imaging in liquid with a significantly extended needle tip.

Atomic force microscope (AFM) probe with a long and rigid needle tip was fabricated and studied for high Q factor dynamic (tapping mode) AFM imaging of samples submersed in liquid. The extended needle tip over a regular commercially available tapping-mode AFM cantilever was sufficiently long to keep the AFM cantilever from submersed in liquid, which significantly minimized the hydrodynamic damping involved in dynamic AFM imaging of samples in liquid. Dynamic AFM imaging of samples in liquid at an intrinsic Q factor of over 100 and an operational frequency of over 200 kHz was demonstrated. The method has the potential to be extended to acquire viscoelastic material properties and provide truly gentle imaging of soft biological samples in physiological environments.

Ion-induced surface relaxation: controlled bending and alignment of nanowire arrays.

It is a well-known fact that a sphere offers less surface area, and thus less surface energy, than any other arrangement of the same volume. From this perspective, all other shapes are metastable objects. In this paper, we present and discuss a manifestation of this metastability: the spontaneous alignment of free-standing amorphous nanowires towards, and ultimately parallel to, a flux of directional ion irradiation. The behavior expected from surface energy reduction is the opposite of that predicted by both theory and experiment regarding defect generation in crystalline nanowires, but is consistent with other observations on non-crystalline materials. We verify our expectations by bending and aligning finely stranded amorphous silica nanowires, noting that such nanostructures are particularly susceptible to bending through ion-induced surface energy reduction. We offer support for this mechanism through bending rate studies, thermal annealing experiments and mathematical modeling. Experimentally, we also demonstrate selective reorientation of nanowires in patterned areas, as well as conformal coating of reoriented arrays with functional materials. These capabilities offer the prospect of exploiting engineered surface anisotropies in optical, fluidic and micromechanical applications.

Energy dissipation and intrinsic loss in single walled carbon nanotubes due to anelastic relaxation.

Based on the molecular dynamics simulation and an elastic shell model, we investigated the intrinsic loss under dynamic excitations in single walled carbon nanotube (SWCNT) due to the anelastic relaxation mechanism. We quantified the anelastic property of SWCNTs, i.e., the creep compliances, and showed them to be on the order of 1 (TPa-1) and sensitive to both the radius of SWCNT and the loading rate. Furthermore, our study showed that the time scale for a SWCNT to fully achieve its equilibrium elastic property through anelastic relaxation is on the order of nanosecond. This leads to significant intrinsic loss and damping for SWCNT resonators operating at the Gigahertz frequency range. Both the loss angle and quality (Q) factor of SWCNT were found to be strongly dependent on the load frequency. A dissipation peak and thus a low Q factor were observed in the Gigahertz frequency range. On the other hand, high Q factor and low dissipation were achieved in the range of low (< 0.001 GHz) excitation frequency. The predicted influence of load frequency on the Q factor is in good agreement with the recent experimental observations.

Biofunctionalized nanoneedles for the direct and site-selective delivery of probes into living cells.

BACKGROUND: Accessing the interior of live cells with minimal intrusiveness for visualizing, probing, and interrogating biological processes has been the ultimate goal of much of the biological experimental development. SCOPE OF REVIEW: The recent development and use of the biofunctionalized nanoneedles for local and spatially controlled intracellular delivery brings in exciting new opportunities in accessing the interior of living cells. Here we review the technical aspect of this relatively new intracellular delivery method and the related demonstrations and studies and provide our perspectives on the potential wide applications of this new nanotechnology-based tool in the biological field, especially on its use for high-resolution studies of biological processes in living cells. MAJOR CONCLUSIONS: Different from the traditional micropipette-based needles for intracellular injection, a nanoneedle deploys a sub-100-nm-diameter solid nanowire as a needle to penetrate a cell membrane and to transfer and deliver the biological cargo conjugated onto its surface to the target regions inside a cell. Although the traditional micropipette-based needles can be more efficient in delivery biological cargoes, a nanoneedle-based delivery system offers an efficient introduction of biomolecules into living cells with high spatiotemporal resolution but minimal intrusion and damage. It offers a potential solution to quantitatively address biological processes at the nanoscale. GENERAL SIGNIFICANCE: The nanoneedle-based cell delivery system provides new possibilities for efficient, specific, and precise introduction of biomolecules into living cells for high-resolution studies of biological processes, and it has potential application in addressing broad biological questions. This article is part of a Special Issue entitled Nanotechnologies - Emerging Applications in Biomedicine.

Nanoneedle: a multifunctional tool for biological studies in living cells.

Studying biology in living cells is methodologically challenging but highly beneficial. Recent advances in nanobiotechnology offer exciting new opportunities to address this challenge. The nanoneedle technology, as an emerging technology that uses a cell membrane-penetrating nanoneedle to probe and manipulate biological processes in living cells, is expected to play an important role in this endeavor. Here we review the recent development and future direction of the nanoneedle technology for biological studies in living cells. The nanoneedle technology is shown to be powerful and versatile, and can offer numerous new ways to explore biological processes and biophysical properties of living cells with high spatial and temporal precision potentially reaching molecular resolution.

Meniscus-confined three-dimensional electrodeposition for direct writing of wire bonds.

Continued progress in the electronics industry depends on downsizing, to a few micrometers, the wire bonds required for wiring integrated chips into circuit boards. We developed an electrodeposition method that exploits the thermodynamic stability of a microscale or nanoscale liquid meniscus to "write" pure copper and platinum three-dimensional structures of designed shapes and sizes in an ambient air environment. We demonstrated an automated wire-bonding process that enabled wire diameters of less than 1 micrometer and bond sizes of less than 3 micrometers, with a breakdown current density of more than 10(11) amperes per square meter for the wire bonds. The technology was used to fabricate high-density and high-quality interconnects, as well as complex three-dimensional microscale and even nanoscale metallic structures.

Tunable, broadband nonlinear nanomechanical resonator.

A nanomechanical resonator incorporating intrinsically geometric nonlinearity and operated in a highly nonlinear regime is modeled and developed. The nanoresonator is capable of extreme broadband resonance, with tunable resonance bandwidth up to many times its natural frequency. Its resonance bandwidth and drop frequency (the upper jump-down frequency) are found to be very sensitive to added mass and energy dissipation due to damping. We demonstrate a prototype nonlinear mechanical nanoresonator integrating a doubly clamped carbon nanotube and show its broadband resonance over tens of MHz (over 3 times its natural resonance frequency) and its sensitivity to femtogram added mass at room temperature.

Nanomechanical heterogeneity in the gap and overlap regions of type I collagen fibrils with implications for bone heterogeneity.

The microstructure of type I collagen, consisting of alternating gap and overlap regions with a characteristic D period of approximately 67 nm, enables multifunctionalities of collagen fibrils in different tissues. Implementing near-surface dynamic and static nanoindentation techniques with atomic force microscope, we reveal mechanical heterogeneity along the axial direction of a single isolated collagen fibril from tendon and show that, within the D period, the gap and overlap regions have significantly different elastic and energy dissipation properties, correlating the significantly different molecular structures in these two regions. We further show that such subfibrillar heterogeneity holds in collagen fibrils inside bone and might be intrinsically related to the excellent energy dissipation performance of bone.

Uncovering nanoscale electromechanical heterogeneity in the subfibrillar structure of collagen fibrils responsible for the piezoelectricity of bone.

Understanding piezoelectricity, the linear electromechanical transduction, in bone and tendon and its potential role in mechanoelectric transduction leading to their growth and remodeling remains a challenging subject. With high-resolution piezoresponse force microscopy, we probed piezoelectric behavior in relevant biological samples at different scale levels: from the subfibrillar structures of single isolated collagen fibrils to bone. We revealed that, beyond the general understanding of collagen fibril being a piezoelectric material, there existed an intrinsic piezoelectric heterogeneity within a collagen fibril coinciding with the periodic variation of its gap and overlap regions. This piezoelectric heterogeneity persisted even for the collagen fibrils embedded in bone, bringing about new implications for its possible roles in structural formation and remodeling of bone.

Nanoscale characterization of isolated individual type I collagen fibrils: polarization and piezoelectricity.

Piezoresponse force microscopy was applied to directly study individual type I collagen fibrils with diameters of approximately 100 nm isolated from bovine Achilles tendon. It was revealed that single collagen fibrils behave predominantly as shear piezoelectric materials with a piezoelectric coefficient on the order of 1 pm V(-1), and have unipolar axial polarization throughout their entire length. It was estimated that, under reasonable shear load conditions, the fibrils were capable of generating an electric potential up to tens of millivolts. The result substantiates the nanoscale origin of piezoelectricity in bone and tendons, and implies also the potential importance of the shear load-transfer mechanism, which has been the principle basis of the nanoscale mechanics model of collagen, in mechanoelectric transduction in bone.

Mechanochemical delivery and dynamic tracking of fluorescent quantum dots in the cytoplasm and nucleus of living cells.

Studying molecular dynamics inside living cells is a major but highly rewarding challenge in cell biology. We present a nanoscale mechanochemical method to deliver fluorescent quantum dots (QDs) into living cells, using a membrane-penetrating nanoneedle. We demonstrate the selective delivery of monodispersed QDs into the cytoplasm and the nucleus of living cells and the tracking of the delivered QDs inside the cells. The ability to deliver and track QDs may invite unconventional strategies for studying biological processes and biophysical properties in living cells with spatial and temporal precision, potentially with molecular resolution.

An improved in situ measurement of offset phase shift towards quantitative damping-measurement with AFM.

An improved approach is introduced in damping measurement with atomic force microscope (AFM) for the in situ measurement of the offset phase shift needed for determining the intrinsic mechanical damping in nanoscale materials. The offset phase shift is defined and measured at a point of zero contact force according to the deflection part of the AFM force plot. It is shown that such defined offset phase shift is independent of the type of sample material, varied from hard to relatively soft materials in this study. This improved approach allows the self-calibrated and quantitative damping measurement with AFM. The ability of dynamic mechanical analysis for the measurement of damping in isolated one-dimensional nanostructures, e.g. individual multiwalled carbon nanotubes, was demonstrated.

Voltage generation from individual BaTiO(3) nanowires under periodic tensile mechanical load.

Direct tensile mechanical loading of an individual single-crystal BaTiO(3) nanowire was realized to reveal the direct piezoelectric effect in the nanowire. Periodic voltage generation from the nanowire was produced by a periodically varying tensile mechanical strain applied with a precision mechanical testing stage. The measured voltage generation from the nanowire was found to be directly proportional to the applied strain rate and was successfully modeled through the consideration of an equivalent circuit for a piezoelectric nanowire under low-frequency operation. The study, besides demonstrating a controlled experimental method for the study of direct piezoelectric effect in nanostructures, implies also the use of such perovskite piezoelectric nanowires for efficient energy-harvesting applications.

Individual nanotube-based needle nanoprobes for electrochemical studies in picoliter microenvironments.

We report the fabrication and characterization of individual nanotube-based, long and straight needle nanoprobes for electrochemistry and the study of their applicability and behavior in microenvironments. The needle nanoprobe, with a nanoscale ring-shaped Au electrode at the tip of the needle serving as the active electrode, was characterized by electrochemical current measurement and cyclic voltammetry and analyzed with electrochemical models. Such a needle nanoprobe, in combination with another metal-coated nanowire as a reference electrode, was further used, for the first time, for local electrochemical sensing inside microdroplets having volumes down to a few picoliters. We explain the acquired voltammetric behaviors of redox-active molecules in confined microscale environments and reveal a unique electrochemical mechanism which allows the regeneration of the redox-active molecules and the establishment of a stable reference potential in the microenvironments.