Resilient silk captures prey in black widow cobwebs

The gumfoot thread of a black widow (Latrodectus hesperus) spider’s cob web is a spring-loaded trap that yanks walking insects into the web. Since spider silks are known as energy dissipating materials, we investigated this trap to find out where the energy is stored. Using previously measured material properties, we modeled the gumfoot thread as a damped harmonic oscillator and compared it to high speed video analysis of prey capture. These measurements show that the gumfoot thread is plastically deformed during prey capture and cannot be the site of energy storage. We then measured the material properties of scaffolding silk that makes up the upper portion of the cob web. Scaffolding silk is highly resilient (90%) at strains less than 3%. This energy storage is sufficient to drive the oscillations seen in prey capture and is consistent with the measured kinematics. This study is the first demonstration of energy-storage as a primary biological function for spider silk. PACS 87.15.La; 81.40.Jj; 81.05.Lg     

Fabrication of black multicrystalline silicon surface by nanosecond laser ablation

The optimal regimes for uniform texturing of a multicrystalline silicon (mc-Si) surface by pulsed laser radiation have been determined. The morphology and reflectance spectra of the texturized mc-Si have been studied. The laser-texturized mc-Si samples with reflectance of 2?C3% over a wide spectral region have been produced. The influence of subsequent chemical etching on the reflective properties of the texturized surface has been analyzed.     

Total x-ray scattering of spider dragline silk

Total x-ray scattering measurements of spider dragline silk fibers from Nephila clavipes, Argiope aurantia, and Latrodectus hesperus all yield similar structure factors, with only small variations between the different species. Wide-angle x-ray scattering from fibers orientated perpendicular to the beam shows a high degree of anisotropy, and differential pair distribution functions obtained by integrating over wedges of the equatorial and meridian planes indicate that, on average, the majority (95%) of the atom-atom correlations do not extend beyond 1 nm. Futhermore, the atom-atom correlations between 1 and 3 nm are not associated with the most intense diffraction peaks at Q=1-2 ?(-1). Disordered molecular orientations along the fiber axis are consistent with proteins in similar structural arrangements to those in the equatorial plane, which may be associated with the silk's greater flexibility in this direction.     

Hierarchical chain model of spider capture silk elasticity

Spider capture silk is a biomaterial with both high strength and high elasticity, but the structural design principle underlying these remarkable properties is still unknown. It was revealed recently by atomic force microscopy that an exponential force-extension relationship holds both for capture silk mesostructures and for intact capture silk fibers [N. Becker et al., Nat. Mater. 2, 278 (2003)]]. In this Letter a simple hierarchical chain model was proposed to understand and reproduce this striking observation. In the hierarchical chain model, a polymer is composed of many structural motifs which organize into structural modules and supramodules in a hierarchical manner. Each module in this hierarchy has its own characteristic force. The repetitive patterns in the amino-acid sequence of the major flagelliform protein of spider capture silk is in support of this model.     

Preparation and mechanical properties of layers made of recombinant spider silk proteins and silk from silk worm

Layers of recombinant spider silks and native silks from silk worms were prepared by spin-coating and casting of various solutions. FT-IR spectra were recorded to investigate the influence of the different mechanical stress occurring during the preparation of the silk layers. The solubility of the recombinant spider silk proteins SO1-ELP, C16, AQ24NR3, and of the silk fibroin from Bombyx mori were investigated in hexafluorisopropanol, ionic liquids and concentrated salt solutions. The morphology and thickness of the layers were determined by Atomic Force Microscopy (AFM) or with a profilometer. The mechanical behaviour was investigated by acoustic impedance analysis by using a quartz crystal microbalance (QCMB) as well as by microindentation. The density of silk layers (d<300 nm) was determined based on AFM and QCMB measurements. At silk layers thicker than 300 nm significant changes of the half-band-half width can be correlated with increasing energy dissipation. Microhardness measurements demonstrate that recombinant spider silk and sericine-free Bombyx mori silk layers achieve higher elastic penetration modules E_EP and Martens hardness values H_M than those of polyethylenterephthalate (PET) and polyetherimide (PEI) foils.     

Tailored ablation processing of advanced biomedical hydroxyapatite by femtosecond laser pulses

The micromachining of hydroxyapatite (HAp) is highly important for orthopedics and dentistry, since human bone and teeth consist mainly of HAp. We demonstrate ultrashort Ti:sapphire laser ablation of HAp, using pulse-widths of 50 fs, 500 fs, and 2 ps at a wavelength of 820 nm and at 1 kpps. The crucial medical issue is to preserve the chemical properties of the machined (ablated) surface. If the chemical properties of HAp change, the human bone or tooth cannot re-grow after laser processing. Using X-ray photoelectron spectroscopy, we observe chemical properties of HAp ablated in air. The HAp is ablated at laser fluences of 3.2 J/cm² (6.4×10¹³ W/cm² at 50 fs), 3.3 J/cm² (6.6×10¹² W/cm² at 500 fs), and 9.6 J/cm² (4.8×10¹² W/cm² at 2 ps), respectively. As a result it is found that the ablated surface is unchanged after laser ablation over the pulse-width range used in this experiment. Received: 7 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +81-45/566-1533, E-mail: obara@obara.elec.keio.ac.jp     

Temperature dependent structure of spider silk by X-ray diffraction

We have investigated the structure of spider dragline silk by X-ray diffraction over a broad temperature range from room temperature up to thermal denaturation conditions. The dominating signal from the β-sheet crystallites is analyzed. Pronounced changes of scattering intensity starting at temperatures around 150 °C are observed. These changes are discussed in view of the respective lattice constants, crystal size, size distribution, crystallite number density and amino acid composition. PACS 87.68.+z; 87.15.-v; 87.64.Bx     

Rheological characterization of hydrogels formed by recombinantly produced spider silk

Many fibrous proteins such as spider silks exhibit impressive mechanical properties and are highly biocompatible leading to many potential biomaterial applications. For applications such as tissue engineering, polymer hydrogels have been proposed as an effective means of producing porous but stable scaffolds. Here, nanofiber-based hydrogels were produced from engineered and recombinantly produced spider silk proteins. The silk nanofibers are stable semi-flexible polymers which assemble into hydrogel networks. We studied the hydrogel rheology and determined the concentration dependence of the elastic modulus. AFM images indicate that the nanofibers might assemble into branch-like structures, which would also be consistent with the measured rheological behavior. Since the developed spider silk hydrogels are stable over weeks and show a high elastic modulus at low volume fractions, they are well suited for a broad variety of applications.     

Processing and modification of films made from recombinant spider silk proteins

Protein films represent an interesting class of materials with various possibilities for applications. We investigated films made of two different synthetic spider silk proteins derived from the garden spider’s (Araneus diadematus) two dragline silk proteins ADF-3 and ADF-4. Protein films cast from hexafluoroisopropanol solutions displayed a predominantly α-helical secondary structure. Processing such films with potassium phosphate or methanol resulted in a transition to a β-sheet rich structure. While as-cast films could be dissolved in water, processed β-sheet rich films were water insoluble. The chemical stability of processed films depended on the amino acid sequence of the respective protein employed. As a proof of principle, fluorescent probes or enzymes were covalently attached to the film surface. The presented approach provides a basis for designing tailor-made protein films using silk proteins as scaffold, in which the film properties can be controlled by genetic engineering of the underlying silks. PACS 68.55.Jk; 81.15.Lm; 87.14.Ee     

Predicting the mechanical properties of spider silk as a model nanostructured polymer

Spider silk is attractive because it is strong and tough. Moreover, an enormous range of mechanical properties can be achieved with only small changes in chemical structure. Our research shows that the full range of thermo-mechanical properties of silk fibres can be predicted from mean field theory for polymers in terms of chemical composition and the degree of order in the polymer structure. Thus, we can demonstrate an inherent simplicity at a macromolecular level in the design principles of natural materials. This surprising observation allows in depth comparison of natural with man-made materials.     

Lithographical laser ablation using femtosecond laser

Lithographical laser ablation was demonstrated using a femtosecond laser with a lithographical optical system. In this method, a femtosecond laser beam passes through a mask and the pattern is imaged on a film by a coherent optical system. As a result, the film is lithographically ablated, and a micron-sized pattern can be generated in a single shot. The resolution of generation was 13 m, and the narrowest width of a generated line was about 4 m. Moreover, the system was applied to transmission gratings as masks, and nano-sized periodic structures such as nano-sized hole matrices and nano-meshes were generated in a single shot. PACS 52.38.Mf; 42.25.Hz; 42.82.Cr; 81.16.-c     

Structural changes of thin films from recombinant spider silk proteins upon post-treatment

Engineering of spider silk proteins offers the possibility to control their molecular sequence and thus their material properties. Spin coating was used to prepare films of engineered spider silk protein derived from the garden spider’s (Araneus diadematus) dragline silk protein ADF-4. A conformational transition from α-helix to β-sheet-rich structures upon methanol treatment of the films was detected by external reflection IR spectroscopy. We present direct evidence for this structural transformation using grazing-incidence X-ray diffraction (GIXRD) and small-angle scattering (GISAXS). The protein film structure after the methanol treatment consists mainly of β-sheet polyalanine crystals dispersed in an amorphous protein matrix. The GIXRD intensity profiles show Bragg peaks from β-sheet polyalanine crystallites having an average size of 7.5 nm. The non-uniform and large crystal size distributions within the film were explained based on the protein composition. The effect of the chemical nature of the interface on the protein film structure was investigated as well. PACS 87.15.-v; 68.55.-a; 61.10.Eq     

Identification and synthesis of novel biomaterials based on spider structural silk fibers

The diversity in function and mechanical behavior of spider silks, and the ability to produce these silks recombinantly, have tremendous potential in creating a new class of biomimetic materials. Here we investigate the structural and mechanical properties of pyriform silks from the golden orb-weaver, Nephila clavipes. Nanoscale indentation measurements using atomic force microscopy on natural pyriform silk suggests that this biomaterial has high toughness that may be suitable for dissipating high amounts of mechanical energy. We also observed the occurrence of highly organized nanocrystals within the pyriform silk fibers that may contribute to the remarkable energy dissipation capability of these silks. It has been demonstrated that poly-(Gly–Ala) and poly-Ala stretches within the internal block repeat modules of dragline silk fibroins form nanocrystals, and these nanocrystalline structures may be responsible for the high extensibility of the dragline silks. In contrast, amino acid sequence analysis shows that PySp2 does not contain the same motifs. In the absence of poly-(Gly–Ala) and poly-Ala repeats, we hypothesized that PySp2 contains new protein motifs sufficient to polymerize into functional structures. To investigate the functional contributions of these novel motifs during pyriform fiber formation, we expressed different recombinant PySp2 fibroins with various segments spanning its block repeat units. We demonstrate that PySp2 recombinant proteins with the Pro-rich sub-block domain (PXP motifs, where X= sub-set of the amino acids A, L, or R) and/or the Ser + Gln + Ala-rich sub-block domain (QQSSVAQS motifs) are sufficient for artificial fiber formation. Moreover, we show that recombinant PySp2 proteins that contain a single block repeat unit can self-assemble into foam-like nanostructures. Collectively, our findings support the use of PySp2 recombinant proteins for a wide range of biomimetic materials with morphologies ranging from fibers to porous structures.     

The first cytogenetic characterization of the poisonous black widow spider Latrodectus gr. curacaviensis from Brazil,with chromosomal review of the family Theridiidae (Arachnida,Araneae)

In this paper we present, for the first time, cytogenetical data on Latrodectus gr. curacaviensis (Theridiidae) from Brazil, as well as the first data on meiosis and sex chromosome system of this genus. Testes were submitted to colchicine, hypotonic, and fixation treatment, and chromosomal preparations were stained with Giemsa solution. The analysis showed 2n = 26 telo/acrocentric chromosomes in spermatogonial metaphases. Metaphase I exhibited 12 autosomal bivalents and two sex chromosome univalents (12II + X₁X₂). All bivalents revealed one terminal chiasma. Metaphases II confirmed the sex chromosome system, showing 12 autosomes or 12 autosomes plus two X chromosomes, respectively. Male karyotype prevailing in theridiids is formed by 2n = 22 chromosomes, including sex chromosome system X₁X₂ in all species. The Latrodectus species of the geometricus clade analyzed until now showed smaller diploid number (2n♀ = 16 and 2n♀ = 18) than the species of the mactans clade (2n♀ = 24 and 2n♀ = 26). Thus, according to the chromosome number, the examined Latrodectus species seems to be related to the mactans clade.     

Precise operation-frequency control of monolithic mode-locked laser diodes for high-speed optical communication and all-optical signal processing

We describe a method for pulse-repetition-frequency tuning of mode-locked laser diodes (MLLDs) monolithically integrated with a distributed Bragg reflector (DBR). The pulse-repetition frequency, i.e., the cavity-roundtrip time, is tuned through loss-induced change in the effective length of the DBR. The frequency-tuning range as large as the chip-to-chip frequency deviation caused by cavity-length fabrication variation of 10 μm has been confirmed experimentally, and the MLLDs operate at SDH (synchronous digital hierarchy) frequencies of 9.953, 19.906 and 39.813 GHz. Synchronization with an external system-clock through the hybrid mode-locking operation reduces the timing jitter of the optical pulses to less than 0.3 ps. As an optical pulse source for optical communication, error-free 20-Gbps transmission over 3000 km has been demonstrated, confirming that the MLLD properties satisfy the requirements for use in real systems. The novel application of MLLDs to all-optical clock extraction, one of the essential functions required in all-optical signal processing, has been demonstrated at the 40-GHz SDH frequency.     

Effect of nonionic surfactant addition on Pyrex glass ablation using water-assisted CO2 laser processing

Pyrex glass etching using laser ablation is an important technology for the microfluid application to lab-on-a-chip devices but suffers from the formation of surface crack. In this article, the addition of nonionic surfactant to water for glass ablation using water-assisted CO₂ laser processing (WACLAP) has been investigated to enhance ablation rate and to eliminate conventional surface defects of cracks in air. WACLAP for Pyrex glass ablation can reduce thermal-stress-induced crack with water cooling and hydrophilic nonionic surfactant to water can enhance ablation performance. Compared to pure water, the 15% weight percent Lauramidopropyl Betaine surfactant solutions for WACLAP can enhance ablation rate from 13.6 to 25 μm/pass of Pyrex glass ablation at a linear laser energy density of 2.11 J/cm, i.e., 24 W power, 114 mm/s scanning speed, and obtain through-wafer etching at 3.16 J/cm for 20 passes without cracks on the surface. Effect of surfactant concentration and linear energy density on WACLAP was also examined. The possible mechanism of surfactant-enhanced phenomenon was discussed by the Newton’s law of viscosity of surfactant solution.     

Micropropulsion using laser ablation

The micro-laser plasma thruster (LPT) is a new micropropulsion device that uses laser ablation to create very small thrusts (0.1–100 N) for pointing and positioning micro- and nano-satellites. In this paper, we discuss the expected performance of the LPT. For a ms-pulse device, target materials are restricted to those of low thermal conductivity, e.g. polymers. Volume ablation theory adequately describes their behavior. In a ns-pulse version, exhaust velocity can be an order of magnitude higher with correspondingly lower thrust-to-power ratio. The theory for surface absorbers describes the observed behavior. PACS 45.55.Px; 42.70.Jk; 52.50.Jm; 42.62.Cf; 42.70.Km; 78.66.Qr     

A proposed ablation laser

A new type of eximer laser is proposed; it involves the simultaneous sublimation and excitation of a frozen film by means of a relativistic electron beam. Calculated beam requirements for noble gases are ～ 10 kA/cm² of 400 kV electrons for periods of 2 to 12 ns. Predicted advantages of this laser are high gain and the elimination of wavelength limiting optical windows. Preliminary experimental fluorescence spectra have been obtained from xenon films. The emission from the solid phase consists primarily of two 100 Å wide bands centered at 1690 Å and 1730 Å the fluorescence lifetimes are 4 ± 2 ns for both bands.     

Superresolved femtosecond laser ablation

The determinist behavior of the femtosecond ablation process allows morphing features well under the diffraction limit by utilizing the thresholding effect, down to the nanometer scale. Because there are a vast range of applications where scaling down the size of the features is a major concern, we investigate the use of superresolving pupil plane filters. As is well known, these filters redistribute the focused optical intensity for a narrower bright spot and, as a trade-off, increase the sidelobes. However, this drawback can be rendered insignificant if all the outer optical power is kept under the determinist threshold value. Two types of pure absorbing binary filter have been tried, giving credence to a size reduction of the ablations in fused silica.