Innovative High-Pressure Fabrication Processes for Porous Biomaterials-A Review.

Biomaterials and their clinical application have become well known in recent years and progress in their manufacturing processes are essential steps in their technological advancement. Great advances have been made in the field of biomaterials, including ceramics, glasses, polymers, composites, glass-ceramics and metal alloys. Dense and porous ceramics have been widely used for various biomedical applications. Current applications of bioceramics include bone grafts, spinal fusion, bone repairs, bone fillers, maxillofacial reconstruction, etc. One of the common impediments in the bioceramics and metallic porous implants for biomedical applications are their lack of mechanical strength. High-pressure processing can be a viable solution in obtaining porous biomaterials. Many properties such as mechanical properties, non-toxicity, surface modification, degradation rate, biocompatibility, corrosion rate and scaffold design are taken into consideration. The current review focuses on different manufacturing processes used for bioceramics, polymers and metals and their alloys in porous forms. Recent advances in the manufacturing technologies of porous ceramics by freeze isostatic pressure and hydrothermal processing are discussed in detail. Pressure as a parameter can be helpful in obtaining porous forms for biomaterials with increased mechanical strength.

Spontaneous formation of multilayer refractory carbide coatings in a molten salt media.

Refractory materials hold great promise to develop functional multilayer coating for extreme environments and temperature applications but require high temperature and complex synthesis to overcome their strong atomic bonding and form a multilayer structure. Here, a spontaneous reaction producing sophisticated multilayer refractory carbide coatings on carbon fiber (CF) is reported. This approach utilizes a relatively low-temperature (950 °C) molten-salt process for forming refractory carbides. The reaction of titanium (Ti), chromium (Cr), and CF yields a complex, high-quality multilayer carbide coating composed of 1) Cr carbide (Cr3C2), 2) Ti carbide, and 3) Cr3C2 layers. The layered sequence arises from a difference in metal dissolutions, reactions, and diffusion rates in the salt media. The multilayer-coated CFs act as a permeable oxidation barrier with no crystalline degradation of the CFs after extreme temperature (1,200 °C) and environment (oxyacetylene flame) exposure. The synthesis of high-quality multilayer refractory coating in a fast, efficient, easy, and clean manner may answer the need for industrial applications that develop cheap and reliable extreme environment protection barriers.

Optimization of highly concentrated dispersions of multi-walled carbon nanotubes with emphasis on surfactant content and carbon nanotubes quality.

Optimized multi-wall carbon nanotubes (MWNT) suspensions in aqueous solution have been obtained by joint use of ultrasonification and surfactant. A simple experimental procedure has been established to efficiently evaluate the dependence of the surfactant concentration on the MWNT concentration stable in suspension. The study of three different surfactants and MWNT provided by three suppliers showed that a threshold surfactant concentration exists above which the MWNT concentration is maximum. Furthermore, it is demonstrated that the maximum MWNT concentration achievable varies from 0.50 to 7.5 g l-1 depending mainly on quality of the MWNT determined by raman spectroscopy analysis.

Laser-induced breakdown spectroscopy of ammonia gas with resonant vibrational excitation.

In this work, laser-induced breakdown spectroscopy (LIBS) of gaseous ammonia (NH3) molecules on- and off-resonant vibrational excitation was studied in open air. A wavelength-tunable, continuous wave (CW), carbon dioxide (CO2) laser tuned at a resonant absorption peak (9.219 µm) within the infrared radiation (IR) range was used to resonantly excite the vibration of the N-H wagging mode of ammonia molecules. A pulsed Nd:YAG laser (1064 nm, 15 ns) was used to break down the ammonia gas for plasma imaging and spectral measurements. In this study, plasmas generated with the ammonia molecules without additional CO2 laser beam irradiation and with additional CO2 laser beam irradiation with the wavelengths on- and off-resonant vibrational excitation of ammonia molecules were investigated and referred as LIBS, LIBS-RE-ON and LIBS-RE-OFF, respectively. The experimental results showed that the temporal and spatial evolution as well as electron temperature and density of plasmas induced with LIBS and LIBS-RE-OFF were consistent but differed from LIBS-RE-ON. Compared with LIBS and LIBS-RE-OFF, plasmas in LIBS-RE-ON showed larger spatial expansion and enhanced emission after a delay time of 1 µs in this study, as well as significantly enhanced electron temperature by ∼ 64%. Time-resolved electron temperatures and densities showed that the emission signal enhancement in LIBS-RE-ON can be primarily attributed to the electron temperature enhancement. Signal enhancement in LIBS indicated improved detection sensitivity. This study could inspire future works on LIBS for gas detection with improved sensitivity and selectivity probably by using ultrafast/intense laser-induced molecular breakdown/ionization with resonant vibrational excitation of molecules.

Aluminum/Carbon Composites Materials Fabricated by the Powder Metallurgy Process.

Aluminum matrix composites reinforced with carbon fibers or diamond particles have been fabricated by a powder metallurgy process and characterized for thermal management applications. Al/C composite is a nonreactive system (absence of chemical reaction between the metallic matrix and the ceramic reinforcement) due to the presence of an alumina layer on the surface of the aluminum powder particles. In order to achieve fully dense materials and to enhance the thermo-mechanical properties of the Al/C composite materials, a semi-liquid method has been carried out with the addition of a small amount of Al-Si alloys in the Al matrix. Thermal conductivity and coefficient of thermal expansion were enhanced as compared with Al/C composites without Al-Si alloys and the experimental values were close to the ones predicted by analytical models.

A Facile Space-Confined Solid-Phase Sulfurization Strategy for Growth of High-Quality Ultrathin Molybdenum Disulfide Single Crystals.

Single-crystal transition metal dichalcogenides (TMDs) and TMD-based heterojunctions have recently attracted significant research and industrial interest owing to their intriguing optical and electrical properties. However, the lack of a simple, low-cost, environmentally friendly, synthetic method and a poor understanding of the growth mechanism post a huge challenge to implementing TMDs in practical applications. In this work, we developed a novel approach for direct formation of high-quality, monolayer and few-layer MoS2 single crystal domains via a single-step rapid thermal processing of a sandwiched reactor with sulfur and molybdenum (Mo) film in a confined reaction space. An all-solid-phase growth mechanism was proposed and experimentally/theoretically evidenced by analyzing the surface potential and morphology mapping. Compared with the conventional chemical vapor deposition approaches, our method involves no complicated gas-phase reactant transfer or reactions and requires very small amount of solid precursors [e.g., Mo (∼3 µg)], no carrier gas, no pretreatment of the precursor, no complex equipment design, thereby facilitating a simple, low-cost, and environmentally friendly growth. Moreover, we examined the symmetry, defects, and stacking phase in as-grown MoS2 samples using simultaneous second-harmonic-/sum-frequency-generation (SHG/SFG) imaging. For the first time, we observed that the SFG (peak intensity/position) polarization can be used as a sensitive probe to identify the orientation of TMDs' crystallographic axes. Furthermore, we fabricated ferroelectric programmable Schottky junction devices via local domain patterning using the as-grown, single-crystal monolayer MoS2, revealing their great potential in logic and optoelectronic applications. Our strategy thus provides a simple, low-cost, and scalable path toward a wide variety of TMD single crystal growth and novel functional device design.

Ultraviolet laser photolysis of hydrocarbons for nondiamond carbon suppression in chemical vapor deposition of diamond films.

In this work, we demonstrate that ultraviolet (UV) laser photolysis of hydrocarbon species alters the flame chemistry such that it promotes the diamond growth rate and film quality. Optical emission spectroscopy and laser-induced fluorescence demonstrate that direct UV laser irradiation of a diamond-forming combustion flame produces a large amount of reactive species that play critical roles in diamond growth, thereby leading to enhanced diamond growth. The diamond growth rate is more than doubled, and diamond quality is improved by 4.2%. Investigation of the diamond nucleation process suggests that the diamond nucleation time is significantly shortened and nondiamond carbon accumulation is greatly suppressed with UV laser irradiation of the combustion flame in a laser-parallel-to-substrate geometry. A narrow amorphous carbon transition zone, averaging 4 nm in thickness, is identified at the film-substrate interface area using transmission electron microscopy, confirming the suppression effect of UV laser irradiation on nondiamond carbon formation. The discovery of the advantages of UV photochemistry in diamond growth is of great significance for vastly improving the synthesis of a broad range of technically important materials.

Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al2O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al2O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O2 chemistry in air.

Thermally Stable and Electrically Conductive, Vertically Aligned Carbon Nanotube/Silicon Infiltrated Composite Structures for High-Temperature Electrodes.

Traditional ceramic-based, high-temperature electrode materials (e.g., lanthanum chromate) are severely limited due to their conditional electrical conductivity and poor stability under harsh circumstances. Advanced composite structures based on vertically aligned carbon nanotubes (VACNTs) and high-temperature ceramics are expected to address this grand challenge, in which ceramic serves as a shielding layer protecting the VACNTs from the oxidation and erosive environment, while the VACNTs work as a conductor. However, it is still a great challenge to fabricate VACNT/ceramic composite structures due to the limited diffusion of ceramics inside the VACNT arrays. In this work, we report on the controllable fabrication of infiltrated (and noninfiltrated) VACNT/silicon composite structures via thermal chemical vapor deposition (CVD) [and laser-assisted CVD]. In laser-assisted CVD, low-crystalline silicon (Si) was quickly deposited at the VACNT subsurfaces/surfaces followed by the formation of high-crystalline Si layers, thus resulting in noninfiltrated composite structures. Unlike laser-assisted CVD, thermal CVD activated the precursors inside and outside the VACNTs simultaneously, which realized uniform infiltrated VACNT/Si composite structures. The growth mechanisms for infiltrated and noninfiltrated VACNT/ceramic composites, which we attributed to the different temperature distributions and gas diffusion mechanism in VACNTs, were investigated. More importantly, the as-farbicated composite structures exhibited excellent multifunctional properties, such as excellent antioxidative ability (up to 1100 °C), high thermal stability (up to 1400 °C), good high velocity hot gas erosion resistance, and good electrical conductivity (∼8.95 Sm-1 at 823 K). The work presented here brings a simple, new approach to the fabrication of advanced composite structures for hot electrode applications.

Systematics and biology of Cotesia typhae sp. n. (Hymenoptera, Braconidae, Microgastrinae), a potential biological control agent against the noctuid Mediterranean corn borer, Sesamia nonagrioides.

Many parasitoid species are subjected to strong selective pressures from their host, and their adaptive response may result in the formation of genetically differentiated populations, called host races. When environmental factors and reproduction traits prevent gene flow, host races become distinct species. Such a process has recently been documented within the Cotesia flavipes species complex, all of which are larval parasitoids of moth species whose larvae are stem borers of Poales. A previous study on the African species C. sesamiae, incorporating molecular, ecological and biological data on various samples, showed that a particular population could be considered as a distinct species, because it was specialized at both host (Sesamia nonagrioides) and plant (Typha domingensis) levels, and reproductively isolated from other C. sesamiae. Due to its potential for the biological control of S. nonagrioides, a serious corn pest in Mediterranean countries and even in Iran, we describe here Cotesia typhae Fernandez-Triana sp. n. The new species is characterized on the basis of morphological, molecular, ecological and geographical data, which proved to be useful for future collection and rapid identification of the species within the species complex. Fecundity traits and parasitism success on African and European S. nonagrioides populations, estimated by laboratory studies, are also included.

Fast Growth of GaN Epilayers via Laser-Assisted Metal-Organic Chemical Vapor Deposition for Ultraviolet Photodetector Applications.

In this study, we successfully developed a carbon dioxide (CO2)-laser-assisted metal-organic chemical vapor deposition (LMOCVD) approach to fast synthesis of high-quality gallium nitride (GaN) epilayers on Al2O3 [sapphire(0001)] substrates. By employing a two-step growth procedure, high crystallinity and smooth GaN epilayers with a fast growth rate of 25.8 µm/h were obtained. The high crystallinity was confirmed by a combination of techniques, including X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and atomic force microscopy. By optimizing growth parameters, the ∼4.3-µm-thick GaN films grown at 990 °C for 10 min showed a smooth surface with a root-mean-square surface roughness of ∼1.9 nm and excellent thickness uniformity with sharp GaN/substrate interfaces. The full-width at half-maximum values of the GaN(0002) X-ray rocking curve of 313 arcsec and the GaN(101̅2) X-ray rocking curve of 390 arcsec further confirmed the high crystallinity of the GaN epilayers. We also fabricated ultraviolet (UV) photodetectors based on the as-grown GaN layers, which exhibited a high responsivity of 0.108 A W-1 at 367 nm and a fast response time of ∼125 ns, demonstrating its high optical quality with potential in optoelectronic applications. Our strategy thus provides a simple and cost-effective means toward fast and high-quality GaN heteroepitaxy growth suitable for fabricating high-performance GaN-based UV detectors.

Facile and Green Reduction of Graphene Oxide by a Reduced Polyoxometalate and Formation of a Nanohybrid.

An ecofriendly chemical reduction of graphene oxide (GO) in water is reported. The reducing agent is an electrochemically reduced Keggin-type polyoxometalate (SiW12 O40 5- ). Moreover, this process leads to the fabrication of SiW12 @rGO nanocomposite. This nanohybrid exhibits an electrochemical response which combines high faradic and capacitive currents due to high coverage of polyoxometalates on the rGO sheets. Therefore this material has strong potentiality for energy storage.

Impact of violated high-dose refuge assumptions on evolution of Bt resistance.

Transgenic crops expressing Bacillus thuringiensis (Bt) toxins have been widely and successfully deployed for the control of target pests, while allowing a substantial reduction in insecticide use. The evolution of resistance (a heritable decrease in susceptibility to Bt toxins) can pose a threat to sustained control of target pests, but a high-dose refuge (HDR) management strategy has been key to delaying countervailing evolution of Bt resistance. The HDR strategy relies on the mating frequency between susceptible and resistant individuals, so either partial dominance of resistant alleles or nonrandom mating in the pest population itself could elevate the pace of resistance evolution. Using classic Wright-Fisher genetic models, we investigated the impact of deviations from standard refuge model assumptions on resistance evolution in the pest populations. We show that when Bt selection is strong, even deviations from random mating and/or strictly recessive resistance that are below the threshold of detection can yield dramatic increases in the pace of resistance evolution. Resistance evolution is hastened whenever the order of magnitude of model violations exceeds the initial frequency of resistant alleles. We also show that the existence of a fitness cost for resistant individuals on the refuge crop cannot easily overcome the effect of violated HDR assumptions. We propose a parametrically explicit framework that enables both comparison of various field situations and model inference. Using this model, we propose novel empiric estimators of the pace of resistance evolution (and time to loss of control), whose simple calculation relies on the observed change in resistance allele frequency.

Multimodal Nonlinear Optical Imaging of MoS2 and MoS2-Based van der Waals Heterostructures.

van der Waals layered structures, notably the transitional metal dichalcogenides (TMDs) and TMD-based heterostructures, have recently attracted immense interest due to their unique physical properties and potential applications in electronics, optoelectronics, and energy harvesting. Despite the recent progress, it is still a challenge to perform comprehensive characterizations of critical properties of these layered structures, including crystal structures, chemical dynamics, and interlayer coupling, using a single characterization platform. In this study, we successfully developed a multimodal nonlinear optical imaging method to characterize these critical properties of molybdenum disulfide (MoS2) and MoS2-based heterostructures. Our results demonstrate that MoS2 layers exhibit strong four-wave mixing (FWM), sum-frequency generation (SFG), and second-harmonic generation (SHG) nonlinear optical characteristics. We believe this is the first observation of FWM and SFG from TMD layers. All three kinds of optical nonlinearities are sensitive to layer numbers, crystal orientation, and interlayer coupling. The combined and simultaneous SHG/SFG-FWM imaging not only is capable of rapid evaluation of crystal quality and precise determination of odd-even layers but also provides in situ monitoring of the chemical dynamics of thermal oxidation in MoS2 and interlayer coupling in MoS2-graphene heterostructures. This method has the advantages of versatility, high fidelity, easy operation, and fast imaging, enabling comprehensive characterization of van der Waals layered structures for fundamental research and practical applications.

Laser-Directed Assembly of Aligned Carbon Nanotubes in Three Dimensions for Multifunctional Device Fabrication.

Laser-directed assembly of multiwalled carbon nanotubes (MWNTs) in 3D space is investigated via a two-photon polymerization technique. MWNT-thiol-acrylate (MTA) composite resins are developed with high MWNT concentrations up to 0.2 wt%, over one order of magnitude higher than previously published work. Significantly enhanced electrical and mechanical properties of the 3D micro-/nanostructures are achieved. Microelectronic devices made of the MTA resins are demonstrated.

Ongoing ecological speciation in Cotesia sesamiae, a biological control agent of cereal stem borers.

To develop efficient and safe biological control, we need to reliably identify natural enemy species, determine their host range, and understand the mechanisms that drive host range evolution. We investigated these points in Cotesia sesamiae, an African parasitic wasp of cereal stem borers. Phylogenetic analyses of 74 individual wasps, based on six mitochondrial and nuclear genes, revealed three lineages. We then investigated the ecological status (host plant and host insect ranges in the field, and host insect suitability tests) and the biological status (cross-mating tests) of the three lineages. We found that one highly supported lineage showed all the hallmarks of a cryptic species. It is associated with one host insect, Sesamia nonagrioides, and is reproductively isolated from the other two lineages by pre- and postmating barriers. The other two lineages had a more variable phylogenetic support, depending on the set of genes; they exhibited an overlapping and diversified range of host species and are not reproductively isolated from one another. We discuss the ecological conditions and mechanisms that likely generated this ongoing speciation and the relevance of this new specialist taxon in the genus Cotesia for biological control.

Phylogenetic molecular species delimitations unravel potential new species in the pest genus Spodoptera Guenée, 1852 (Lepidoptera, Noctuidae).

Nowadays molecular species delimitation methods promote the identification of species boundaries within complex taxonomic groups by adopting innovative species concepts and theories (e.g. branching patterns, coalescence). As some of them can efficiently deal with large single-locus datasets, they could speed up the process of species discovery compared to more time consuming molecular methods, and benefit from the existence of large public datasets; these methods can also particularly favour scientific research and actions dealing with threatened or economically important taxa. In this study we aim to investigate and clarify the status of economically important moths species belonging to the genus Spodoptera (Lepidoptera, Noctuidae), a complex group in which previous phylogenetic analyses and integrative approaches already suggested the possible occurrence of cryptic species and taxonomic ambiguities. In this work, the effectiveness of innovative (and faster) species delimitation approaches to infer putative species boundaries has been successfully tested in Spodoptera, by processing the most comprehensive dataset (in terms of number of species and specimens) ever achieved; results are congruent and reliable, irrespective of the set of parameters and phylogenetic models applied. Our analyses confirm the existence of three potential new species clusters (for S. exigua (Hübner, 1808), S. frugiperda (J.E. Smith, 1797) and S. mauritia (Boisduval, 1833)) and support the synonymy of S. marima (Schaus, 1904) with S. ornithogalli (Guenée, 1852). They also highlight the ambiguity of the status of S. cosmiodes (Walker, 1858) and S. descoinsi Lalanne-Cassou & Silvain, 1994. This case study highlights the interest of molecular species delimitation methods as valuable tools for species discovery and to emphasize taxonomic ambiguities.

Food searching behaviour of a Lepidoptera pest species is modulated by the foraging gene polymorphism.

The extent of damage to crop plants from pest insects depends on the foraging behaviour of the insect's feeding stage. Little is known, however, about the genetic and molecular bases of foraging behaviour in phytophagous pest insects. The foraging gene (for), a candidate gene encoding a PKG-I, has an evolutionarily conserved function in feeding strategies. Until now, for had never been studied in Lepidoptera, which includes major pest species. The cereal stem borer Sesamia nonagrioides is therefore a relevant species within this order with which to study conservation of and polymorphism in the for gene, and its role in foraging - a behavioural trait that is directly associated with plant injuries. Full sequencing of for cDNA in S. nonagrioides revealed a high degree of conservation with other insect taxa. Activation of PKG by a cGMP analogue increased larval foraging activity, measured by how frequently larvae moved between food patches in an actimeter. We found one non-synonymous allelic variation in a natural population that defined two allelic variants. These variants presented significantly different levels of foraging activity, and the behaviour was positively correlated to gene expression levels. Our results show that for gene function is conserved in this species of Lepidoptera, and describe an original case of a single nucleotide polymorphism associated with foraging behaviour variation in a pest insect. By illustrating how variation in this single gene can predict phenotype, this work opens new perspectives into the evolutionary context of insect adaptation to plants, as well as pest management.

Simulating population genetics of pathogen vectors in changing landscapes: guidelines and application with Triatoma brasiliensis.

BACKGROUND: Understanding the mechanisms that influence the population dynamics and spatial genetic structure of the vectors of pathogens infecting humans is a central issue in tropical epidemiology. In view of the rapid changes in the features of landscape pathogen vectors live in, this issue requires new methods that consider both natural and human systems and their interactions. In this context, individual-based model (IBM) simulations represent powerful yet poorly developed approaches to explore the response of pathogen vectors in heterogeneous social-ecological systems, especially when field experiments cannot be performed. METHODOLOGY/PRINCIPAL FINDINGS: We first present guidelines for the use of a spatially explicit IBM, to simulate population genetics of pathogen vectors in changing landscapes. We then applied our model with Triatoma brasiliensis, originally restricted to sylvatic habitats and now found in peridomestic and domestic habitats, posing as the most important Trypanosoma cruzi vector in Northeastern Brazil. We focused on the effects of vector migration rate, maximum dispersal distance and attraction by domestic habitat on T. brasiliensis population dynamics and spatial genetic structure. Optimized for T. brasiliensis using field data pairwise fixation index (FST) from microsatellite loci, our simulations confirmed the importance of these three variables to understand vector genetic structure at the landscape level. We then ran prospective scenarios accounting for land-use change (deforestation and urbanization), which revealed that human-induced land-use change favored higher genetic diversity among sampling points. CONCLUSIONS/SIGNIFICANCE: Our work shows that mechanistic models may be useful tools to link observed patterns with processes involved in the population genetics of tropical pathogen vectors in heterogeneous social-ecological landscapes. Our hope is that our study may provide a testable and applicable modeling framework to a broad community of epidemiologists for formulating scenarios of landscape change consequences on vector dynamics, with potential implications for their surveillance and control.

Strong discrepancies between local temperature mapping and interpolated climatic grids in tropical mountainous agricultural landscapes.

Bridging the gap between the predictions of coarse-scale climate models and the fine-scale climatic reality of species is a key issue of climate change biology research. While it is now well known that most organisms do not experience the climatic conditions recorded at weather stations, there is little information on the discrepancies between microclimates and global interpolated temperatures used in species distribution models, and their consequences for organisms' performance. To address this issue, we examined the fine-scale spatiotemporal heterogeneity in air, crop canopy and soil temperatures of agricultural landscapes in the Ecuadorian Andes and compared them to predictions of global interpolated climatic grids. Temperature time-series were measured in air, canopy and soil for 108 localities at three altitudes and analysed using Fourier transform. Discrepancies between local temperatures vs. global interpolated grids and their implications for pest performance were then mapped and analysed using GIS statistical toolbox. Our results showed that global interpolated predictions over-estimate by 77.5 ± 10% and under-estimate by 82.1 ± 12% local minimum and maximum air temperatures recorded in the studied grid. Additional modifications of local air temperatures were due to the thermal buffering of plant canopies (from -2.7 °K during daytime to 1.3 °K during night-time) and soils (from -4.9 °K during daytime to 6.7 °K during night-time) with a significant effect of crop phenology on the buffer effect. This discrepancies between interpolated and local temperatures strongly affected predictions of the performance of an ectothermic crop pest as interpolated temperatures predicted pest growth rates 2.3-4.3 times lower than those predicted by local temperatures. This study provides quantitative information on the limitation of coarse-scale climate data to capture the reality of the climatic environment experienced by living organisms. In highly heterogeneous region such as tropical mountains, caution should therefore be taken when using global models to infer local-scale biological processes.