Microwave induced mechanical activation of hydrogel dimers.

When grape-sized aqueous dimers are irradiated in a microwave oven, an intense electromagnetic hotspot forms at their point of contact, often igniting a plasma. Here we show that this irradiation can result in the injection of mechanical energy. By examining irradiated hydrogel dimers through high-speed imaging, we find that they repeatedly bounce off of each other while irradiated. We determine that an average of 1 µJ of mechanical energy is injected into the pair during each collision. Furthermore, a characteristic high-pitched audio signal is found to accompany each collision. We show that both the audio signal and the energy injection arise via an interplay between vaporization and elastic deformations in the region of contact, the so-called 'elastic Liedenfrost effect'. Our results establish a novel, non-contact method of injecting mechanical energy into soft matter systems, suggesting application in fields such as soft robotics.

Linking plasma formation in grapes to microwave resonances of aqueous dimers.

The sparking of cut grape hemispheres in a household microwave oven has been a poorly explained Internet parlor trick for over two decades. By expanding this phenomenon to whole spherical dimers of various grape-sized fruit and hydrogel water beads, we demonstrate that the formation of plasma is due to electromagnetic hotspots arising from the cooperative interaction of Mie resonances in the individual spheres. The large dielectric constant of water at the relevant gigahertz frequencies can be used to form systems that mimic surface plasmon resonances that are typically reserved for nanoscale metallic objects. The absorptive properties of water furthermore act to homogenize higher-mode profiles and to preferentially select evanescent field concentrations such as the axial hotspot. Thus, beyond providing an explanation for a popular-science phenomenon, we outline a method to experimentally model subwavelength field patterns using thermal imaging in macroscopic dielectric systems.

Spectrally-broad coherent anti-Stokes Raman scattering hyper-microscopy utilizing a Stokes supercontinuum pumped at 800 nm.

We demonstrate spectral-focusing based coherent anti-Stokes Raman scattering (SF-CARS) hyper-microscopy capable of probing vibrational frequencies from 630 cm-1 to 3250 cm-1 using a single Ti:Sapphire femtosecond laser operating at 800 nm, and a commercially-available supercontinuum-generating fibre module. A broad Stokes supercontinuum with significant spectral power at wavelengths between 800 nm and 940 nm is generated by power tuning the fibre module using atypically long and/or chirped ~200 fs pump pulses, allowing convenient access to lower vibrational frequencies in the fingerprint spectral region. This work significantly reduces the instrumental and technical requirements for multimodal CARS microscopy, while expanding the spectral capabilities of an established approach to SF-CARS.

Benford's Law: textbook exercises and multiple-choice testbanks.

Benford's Law describes the finding that the distribution of leading (or leftmost) digits of innumerable datasets follows a well-defined logarithmic trend, rather than an intuitive uniformity. In practice this means that the most common leading digit is 1, with an expected frequency of 30.1%, and the least common is 9, with an expected frequency of 4.6%. Currently, the most common application of Benford's Law is in detecting number invention and tampering such as found in accounting-, tax-, and voter-fraud. We demonstrate that answers to end-of-chapter exercises in physics and chemistry textbooks conform to Benford's Law. Subsequently, we investigate whether this fact can be used to gain advantage over random guessing in multiple-choice tests, and find that while testbank answers in introductory physics closely conform to Benford's Law, the testbank is nonetheless secure against such a Benford's attack for banal reasons.

Label-free hyperspectral nonlinear optical microscopy of the biofuel micro-algae Haematococcus Pluvialis.

We consider multi-modal four-wave mixing microscopies to be ideal tools for the in vivo study of carotenoid distributions within the important biofuel microalgae Haematococcus pluvialis. We show that hyperspectral coherent anti-Stokes Raman scattering (CARS) microscopy generates non-invasive, quantitative real-time concentrations maps of intracellular carotenoid distributions in live algae.

Hyperspectral multimodal CARS microscopy in the fingerprint region.

A simple scheme for multimodal coherent anti-Stokes Raman scattering (CARS) microscopy is based on the spectral focusing of ultrafast-oscillator-derived pump/probe light and synchronous photonic crystal fiber (PCF) fiber-generated broadband Stokes light. To date, such schemes allowed rapid hyperspectral imaging throughout the CH/OH high frequency region (2700-4000 cm(-1) ). Here we extend this approach to the middle (1640-3300 cm(-1) ) and fingerprint regions (850-1800 cm(-1) ) of the Raman spectrum. Our simple integrated approach to rapid hyperspectral CARS microscopy in the fingerprint region is demonstrated by applications to label-free multimodal imaging of cellulose and bulk bone, including use of the phosphate resonance at 960 cm(-1) .

Spatial-spectral coupling in coherent anti-Stokes Raman scattering microscopy.

Coherent anti-Stokes Raman scattering (CARS) microscopy is a third-order nonlinear optical technique which permits label-free, molecule-specific hyperspectral imaging. The interference between coherent resonant and non-resonant terms leads to well known distortions in the vibrational spectrum, requiring the use of retrieval algorithms. It also leads to spatial imaging distortions, largely due to the Gouy phase, when objects are smaller than the Rayleigh range. Here we consider that the focal position and spectral contributions to the nonlinear image formation are intrinsically coupled and cannot be corrected by conventional retrieval methods.

Pulse splitting in the anomalous group-velocity-dispersion regime.

We investigate experimentally the role that the initial temporal profile of ultrashort laser pulses has on the self-focusing dynamics in the anomalous group-velocity dispersion (GVD) regime. We observe that pulse-splitting occurs for super-Gaussian pulses, but not for Gaussian pulses. The splitting does not occur for either pulse shape when the GVD is near-zero. These observations agree with predictions based on the nonlinear Schrödinger equation, and can be understood intuitively using the method of nonlinear geometrical optics.

Forward-collected simultaneous fluorescence lifetime imaging and coherent anti-Stokes Raman scattering microscopy.

We demonstrate the simultaneous collection and separation of femtosecond-laser-based forward-collected coherent anti-Stokes Raman scattering (F-CARS) and two-photon-excitation-induced fluorescence lifetime images (FLIM) using time-correlated single photon counting (TCSPC). We achieve this in a nondescanned geometry using a single multimode fiber without significant loss of light, field of view, and most importantly, TCSPC timing fidelity. In addition to showing the ability to separate CARS images from FLIM images using time gating, we also demonstrate composite multimodal epicollected FLIM imaging with fiber-collected F-CARS imaging in live cells.

Two-photon absorption properties of two-dimensional π-conjugated chromophores: combined experimental and theoretical study.

The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis.

Single laser source for multimodal coherent anti-Stokes Raman scattering microscopy.

Short laser pulse technology has significantly contributed to biomedical research, especially via nonlinear optical microscopy. Coherent anti-Stokes Raman scattering (CARS) microscopy is a label-free, chemical-selective method that is growing in importance as improved methods and light sources develop. Here we discuss different approaches to laser source development for CARS microscopy and highlight the advantages of a multimodal CARS microscope, illustrated by selected applications in biomedical research.

All-optical modulation of four-wave mixing in an Rb-filled photonic bandgap fiber.

We demonstrate efficient all-optical modulation using Rb vapor confined to a hollow-core photonic bandgap fiber. The intensity of a signal field participating in the four-wave-mixing process is modulated using a weak switching field. We observe 3 dB of attenuation in the signal field with only 3600 photons of switching energy, corresponding to 23 photons per atomic cross section lambda(2)/(2pi). Modulation bandwidths as high as 300 MHz are observed.

Multimodal CARS microscopy of structured carbohydrate biopolymers.

We demonstrate the utility of multimodal coherent anti-Stokes Raman scattering (CARS) microscopy for the study of structured condensed carbohydrate systems. Simultaneous second-harmonic generation (SHG) and spectrally-scanned CARS microscopy was used to elucidate structure, alignment, and density in cellulose cotton fibers and in starch grains undergoing rapid heat-moisture swelling. Our results suggest that CARS response of the O-H stretch region (3000 cm(-1)-3400 cm(-1)), together with the commonly-measured C-H stretch (2750 cm(-1)-2970 cm(-1)) and SHG provide potentially important structural information and contrast in these materials.

Ultralow-power four-wave mixing with Rb in a hollow-core photonic band-gap fiber.

We demonstrate extremely efficient four-wave mixing with gains greater than 100 at microwatt pump powers and signal-to-idler conversion of 50% in Rb vapor confined to a hollow-core photonic band-gap fiber. We present a theoretical model that demonstrates such efficiency is consistent with the dimensions of the fiber and the optical depths attained. This is, to our knowledge, the largest four-wave mixing gain observed at such low total pump powers and the first demonstrated example of four-wave mixing in an alkali-metal vapor system with a large (approximately 30 MHz) ground state decoherence rate.

Generation of large alkali vapor densities inside bare hollow-core photonic band-gap fibers.

We demonstrate the ability to generate extremely large rubidium densities in uncoated hollow-core photonic band-gap fibers using light-induced atomic desorption. Once the fiber is exposed to Rb vapor for 1-2 weeks, and this atomic source is removed, the fiber yields large desorbable densities for an extended period of time. We show that optical depths greater than e(-1200) can be created within seconds. Our observed Rb densities are several orders of magnitude larger than any previously reported to be generated optically, and allow for the demonstration of a relatively easy-to-use fiber-based vapor cell capable of producing large optical depths without the need for thermal tuning.

Absorption of ultrashort optical pulses in water.

We investigate the linear propagation of 800 and 1530 nm ultrashort optical pulses in water. For all pulse repetition rates studied, we observe pure exponential decay down to a transmission of 2.5 x 10(-5). We further demonstrate that previous observations of nonmonoexponential decay and pulse splitup in broadband pulses are consistent with Beer's law in the purely linear regime.

Two-photon absorption in two-dimensional conjugated quadrupolar chromophores.

We present ultrafast z-scan measurements of the two-photon absorption (TPA) spectra of a pair of two-dimensionally conjugated quadrupolar donor/acceptor (D/A) chromophores. The all-donor substituted species displays a peak TPA cross section [sigma(2)=520+/-30 GM] that is more than twice that of the D-A species [sigma(2)=240+/-20 GM]. Unlike previous structure-property studies that have evaluated TPA behavior for D/A molecules through the comparison of dipolar and quadrupolar compounds, both molecules investigated herein are quadrupolar, ultimately providing a more consistent evaluation of the effects of donor and/or acceptor substitution on the TPA of conjugated chromophores.

Synthesis, spectroscopic and nonlinear optical properties of multiple [60]fullerene-oligo(p-phenylene ethynylene) hybrids.

A series of multiple [60]fullerene terminated oligo(p-phenylene ethynylene) (OPE) hybrid compounds has been synthesized through a newly developed in situ ethynylation method. Structural and magnetic shielding properties of the highly unsaturated carbon-rich C(60) and OPE scaffolds were characterized by 1D and 2D NMR spectroscopic analyses. Electronic interactions between the [60]fullerenes and the OPE backbones were investigated by UV/Vis spectroscopic and cyclic voltammetry (CV) experiments. Our studies clearly show that although the multiple [60]fullerene groups are connected via pi-conjugated OPE frameworks, they present diminutive electronic interactions in the ground state, and the electronic behavior of the [60]fullerene cages are only affected by the OPE backbones through modest inductive effects. Interestingly, sizable third-order nonlinear optical (NLO) responses (gamma) and enhanced two-photon absorption (TPA) cross-sections (sigma((2))) were determined for the multifullerene-OPE hybrid 31 relative to its OPE precursor from differential optical Kerr effect (DOKE) experiments. Such enhanced NLO performance is presumably due to the occurrence of periconjugation and/or charge transfer effects in the excited state. In addition, comparatively strong excited-state absorption was observed and characterized for OPE pentamer 12. Thus, the use of such fullerene-derivatized conjugated oligomers aids the quest for molecules with large third-order NLO and TPA properties.

Polyynes as a model for carbyne: synthesis, physical properties, and nonlinear optical response.

With the Fritsch-Buttenberg-Wiechell rearrangement as a primary synthetic route, a series of conjugated, triisopropylsilyl end-capped polyynes containing 2-10 acetylene units has been assembled. In a few steps, significant quantities of the polyynes are made available, which allow for a thorough analysis of their structural, physical, and optical properties. Molecules in the series have been characterized in detail using (13)C NMR spectroscopy, differential scanning calorimetry, mass spectrometry, and, for four derivatives including octayne 6, X-ray crystallography. UV-vis spectroscopy of the polyynes 1-7 shows a consistent lowering of the HOMO-LUMO gap (E(g)) as a function of the number of acetylene units (n), fitting a power-law relationship of E(g) approximately n(-)(0.379)(+/-)(0.002). The third-order nonlinear optical (NLO) properties of the polyyne series have been examined, and the nonresonant molecular second hyperpolarizabilities (gamma) increase as a function of length according to the power-law gamma approximately n(4.28)(+/-)(0.13). This result exhibits an exponent that is larger than theoretically predicted for polyynes and higher than is observed for polyenes and polyenynes. The combined linear and nonlinear optical results confirm recent theoretical studies that suggest polyynes as model 1-D conjugated systems. On the basis of UV-vis spectroscopic analysis, the effective conjugation length for this series of polyynes is estimated to be ca. n = 32, providing insight into characteristics of carbyne.

Synthesis, structure, and nonlinear optical properties of diarylpolyynes.

A series of alpha,omega-diarylpolyynes has been synthesized. In addition to the synthesis of three hexaynes (3a-c), a notably improved synthesis of 1,16-diphenylhexadecaoctayne (5) is described. The third-order nonlinear optical characteristics for these molecules have been studied and show a substantial increase in molecular hyperpolarizability (gamma) as a function of increasing length. The unusual solid-state structures of compounds 3a and 3b are reported.