Focused Session CB-8
Bio-inspired and Bio-enabled Processing
ABSTRACTS
Session CB-8.1 - Self-assembly, mineralization and hierarchical organization; hybrid structures
CB-8.1:IL01 Designed Construction of Nanostructured Inorganic and Hybrid Materials: Similarities between Natural & Synthetic Approaches
C. SANCHEZ, Collège de France, Lab. de Chimie de la Matière Condensée de Paris, CNRS, Université Pierre et Marie Curie, Paris, France
For the past five hundred million years nature has produced materials with remarkable properties and features such as the smart functionnal surfaces found in some leaves and flowers, the beautifully carved structures found in radiolaria or diatoms, the extraordinary mechanical and self-healing properties found in many composites. Another of nature’s remarkable features is its ability to combine at the nanoscale (bio) organic and inorganic components allowing the construction of smart natural hybrid materials. To day bottum-up strategies also allow to design the so-called hybrid organic–inorganic materials where organic and inorganic components are intimately mixed. Hybrid materials based stategies are today generating smart membranes, new catalysts and sensors, new generation of photovoltaic and fuel cells, smart microelectronic, micro-optical and photonic components and systems, or intelligent therapeutic vectors that combine targeting, imaging, therapy and controlled release properties. This invited lecture will present in particular analogies between, engineering and processing made by nature to construct performant materials and the today strategies used by materials chemists and engineers to produce modern materials through a kind of controlled design will be emphasized.
CB-8.1:IL02 Protein-based Functionalization of Diatom Biosilica
N. KROEGER, E. KUMARI, N. DUBEY, G. BEGUM, B CUBE Center for Molecular Bioengineering, Dresden University of Technology, Dresden, Germany
Diatoms are single-celled microalgae that produce cell walls made of amorphous hydrated SiO2. The biosilica produced by diatoms is a remarkable biological material, because it has highly porous and open 3D structures and yet exhibits remarkably high mechanical stability. The hierarchically arranged pores typically range from about 10 nm to several hundred of nm in diameter, which gives rise to interesting optical phenomena and allows for rapid mass transport through the material. During the past two decades it has been realized that the properties of diatom biosilica can be harnessed and further enhanced by introducing inorganic, organic, and biomolecular moieties, which provide key functionalities for diatom nanotechnology. Here I will present recent advances in functionalizing diatom biosilica with enzymes and receptor proteins, and describe the properties and applications of the resulting materials.
CB-8.1:IL04 Chemical Transformation of Sustainable 3-D Microscale Biogenic Structures into High-Fidelity Replicas Comprised of Multicomponent Functional Synthetic Materials
K.H. SANDHAGE, School of Materials Engineering, Purdue University, West Lafayette, IN, USA
Hierarchically-patterned rigid biogenic structures with a variety of intricate morphologies can be found throughout nature. Certain biological organisms are adept at generating enormous numbers of microscale structures with complex, yet well-controlled shapes decorated with fine (down to nanoscale) patterned features. Such sustainable mass production of 3-D microscale/nanostructured assemblies would be highly attractive for a number of advanced technologies, if such assemblies could be generated with desired synthetic (non-naturally-occurring) inorganic chemistries. In this presentation, two strategies will be described for transforming sustainable 3-D bio-inorganic and bio-organic microparticle templates into replicas comprised of multicomponent synthetic functional inorganic materials. Shape-preserving gas/solid reactions have been used to transform the microscale silica frustules of diatoms (unicellular algae) into high-fidelity replicas comprised of a variety of other oxide and non-oxide inorganic materials. The layer-by-layer deposition of thin, highly-conformal inorganic coatings, followed by thermal treatment (to allow for organic pyrolysis and oxide crystallization), has been used to transform pollen grains into multicomponent oxide particles that retain the overall pollen morphology and fine surface features. The reactions and micro/nanostructural evolution associated with both chemical conversion strategies, and the properties of the resulting biogenic/synthetic microparticles, will be discussed.
CB-8.1:IL05 Designing Hierarchical Rare Earth Nanoceramics for Biomedical Applications
S. SEAL, Materials Science & Eng, Advanced Materials Processing Analysis Center, Nanoscience Technology Center, College of Medicine, University of Central Florida, Orlando, Fl, USA
Nanostructured materials are proved to have unique structures with a plethora of applications in biomedical arena. Particularly, nanoceria (CNPs) is the one recently finding its way in various medical usage. The fundamental mechanism is attributed to the antioxidant property of CNPs in oxidation/reduction milieu, resulting from switching of the oxidation states from Ce3+ to Ce4+ and making it redox active. However, we have seen that the surface chemistry is governed by the ratio of Ce3+/Ce4+ and can be extensively modulated by the assembly process. We have synthesized ceria nanoparticles in various medium and studied their self-assembly process to octahedral and star shaped structures through hierarchical design. It was further identified that the concentration of Ce4+ in nanoceria varies over time, further controlling the surface chemistry. Also, we have investigated the self-assembly of CeO2 into nanorods in ice and the experiments are validated through computer simulation. It has been established that nanoceria mimic the naturally existing enzymes in the body namely, catalase and superoxide dismutase (SOD). We will conclude the talk with few examples of nanoceria applications in reduction of chronic inflammation, protecting tissues against radiation protection, aid in inhibiting laser induced retinal damage, etc.
CB-8.1:L06 Nonclassical Crystallization in Vivo: A Fundamental Process-structure-property Relationship in Biominerals and New Synthesis Pathway to Bioinspired Nanoceramics and Gradient Materials
S.E. WOLF, Institute for Glass and Ceramics, Friedrich-Alexander-University Erlangen-Nürnberg, Erlangen, Germany
Well-known for structural wealth on the macro- to the mesoscale, apparently all biominerals share a distinct nanogranular fine structure. This feature not only affects a remarkable number of properties of the bioceramic material, moreover, the nanogranularity roots in a common and nonclassical growth mode, as we recently demonstrated for bivalve nacre. This finding enables us to state a fundamental process-structure-property relationship in biominerals which may spark new design routes to biomimetic smart materials. We demonstrate further that ACC can pseudomorphically transform allowing incorporation of various inorganic additives. This gives rise to a nanoscale structure indiscernible from the biogenic counterpart and allows tuning of the final mineral composition, paving the way to a new field of crystal design. In a comparative case study, we show that the interplay between transforming mineral phase and organic inclusions give rise to crystal lattice twisting and tilting.The showcase of a bivalve shell demonstrates that this approach can be ultimately employed as new means to generate gradient materials unparalleled by mankind.
CB-8.1:L07 Bioprocess Inspired Synthesis of Functional Materials
HAO XIE1, 2, Zheng-Yi Fu1, 1State Key Lab of Advanced Technology for Materials Synthesis and Processing; 2School of Chemistry, Chemical Engineering, and Life Science, Wuhan University of Technology, Wuhan, China
Biological processes are vital for living organisms in producing biomaterials with elegant structures as well as unique functions and properties. A biological process is usually made up of a series of sequential biochemical reactions relying on functional proteins or enzymes. Biomineralization is a typical biological process in which mineral proteins template and/or regulate the formation and morphology of biominerals. Learning from biomineralization processes, we investigated the bioprocess inspired technology for synthesizing functional materials. Firstly, we explored the construction of recombinant proteins by combing mineral protein domains to optimize and integrate biomineralization processes. Then, we constructed confined biomineralization environments by genetically displaying reorganized functional domains of mineral proteins on the bacterial surface to integrate biomineralization processes for producing nanostructured electrode materials such as TiO2 or SnO2. Significant improvements of electrochemical performance were observed with the synthesized materials. The synthesis process and products were controllable by adjusting displayed protein domains. These results demonstrate the protein/enzyme-based integration of biological processes for producing functional materials.
Session CB-8.2 - Structure and Mechanics of Bioinspired Materials
CB-8.2:IL01 Strain-rate Dependent Deformation Mechanism of Bioinspired Graphene-Al Nanolaminated Composites
QIANG GUO, LEI ZHAO, ZAN LI, ZHIQIANG LI, GENLIAN FAN, DING-BANG XIONG, YISHI SU, DI ZHANG, State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, China
Nanolaminated structure is widely adopted by hard biological materials, which, by taking advantage of the high strength of nano-scaled constituent phases and the various toughening mechanisms provided by the laminated structure, are shown to be both strong and damage-tolerant. In this study, we carried out uniaxial compression tests conducted at various strain rates, to uncover the strain-rate dependent deformation mechanism of micro-pillars fabricated from nanolaminated graphene-Al composites. It was found that in both compositeand pure Al pillars, compression at high strain rates resulted in relatively smooth stress-strain response, as opposed to the jerky deformation at low strain rates. At any given strain rate, the composite pillars had significantly higher strengths than their pure Al counterparts, and this reinforcing effect became more pronounced with increasing strain rate. Also, the composite pillars were characterized by considerably higher strain rate sensitivity index and correspondingly lower activation volume than the pure Al pillars. These observations were interpreted by a competition between dislocation generation and annihilation, a transition in the deformation mechanism over different strain rates, and the dislocation obstruction by the graphene/Al interfaces.
CB-8.2:IL02 High-throughput Bioengineering of Novel Nanostructures by Genetic Manufacturing on Insect Corneal Surfaces: Looking for Applications
V. KATANAEV, University of Lausanne, Lausanne, Switzerland
Corneal surfaces of terrestrial insects are covered with elaborate nanocoatings. Initially described as moth-eye nanostructures –nipple-like evaginations regularly assembled on the lenses of some Lepidopterans – they were in recent years discovered to be omnipresent across insect lineages. In addition to the nipple-type morphology, corneal nanocoatings can be built as ridge-, maze-, or dimple-type nanopatterns. Varying in the height of dozens to hundreds nanometers, and in the diameter being thinner than the wavelength of the visible light, these nanostructures provide the antireflective function to the surfaces they coat. Turing reaction-diffusion mechanism of molecular self-assembly has been proposed to guide the formation of the corneal nanostructures. This mechanism envisions interactions of two types of molecular agents with different properties as the underlying principle of building of the nanostructures. Using model insect organisms, molecular identities of these agents can be revealed. These studies will elucidate the mechanism of formation and diversity of the corneal nanostructures in arthropods. Further, they will lay the ground for bioengineering, in vivo and in vitro, of novel nanocoatings with desired properties.
CB-8.2:IL04 Architecture and Interface Design for Multifunctional Graphene/Copper Matrix Composites
DING-BANG XIONG, MU CAO, ZHIQIANG LI, DI ZHANG, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, China
Recently, tailoring properties by architecture design that changes the spatial distribution of reinforcement in matrix at micro-/nano-scale without changing constituents has attracted intensive attention in the community of composite. Natural biological materials are characterized by combining simple constituents into a wide variety of composites with a maximum of control over architecture on many length scales, exhibiting a remarkable range of mechanical and functional properties. Understanding the role that multilevel architectures play in controlling properties of natural materials may serve as inspirations for architecture design in composites. Metals can be strengthened by adding hard reinforcements, but such strategy usually compromises ductility and toughness as well as electrical/thermal conductivity. In past few years, a bioinspired strategy has been applied to surmount the dilemma in our research. By assembling copper nanoflakes cladded with graphene, graphene/copper matrix composites with a natural nacre inspired nanolaminated architecture have been prepared. Owing to a combined effect from the bioinspired nanolaminated architecture and improved interface bonding, a synergism has been made between mechanical strength and ductility as well as electrical/thermal conductivity in graphene/copper matrix composites. The bioinspired nanolaminated architecture enhances the mechanical strengthening and electrical/thermal conducting efficiencies of two-dimensional graphene by alignment of graphene that orient to maximize performance for required loading and carrier transporting conditions, and toughening by crack deflection. The strategy sheds light on the development of structural-multifunctional integrated composites.
References: [1] Xiong, D.B.; Cao, M.; Guo, Q.; Tan, Z.Q.; Fan, G.L.; Li, Z.Q.; Zhang, D. ACS Nano, 9 (2015) 6934–6943; [2] Xiong, D.B.; Cao, M.; Guo, Q.; Tan, Z.Q.; Fan, G.L.; Li, Z.Q.; Zhang, D. Scientific Reports, 6 (2016) 33801; [3] Cao, M.; Xiong, D.B.; Tan, Z.Q.; Ji G.; Amin-Ahmadi .; Fan, G.L.; Guo, Q.;Li, Z.Q.; Zhang, D. Carbon,117 (2017) 65-74; [4] Zhao M.; Xiong D.B.; Tan, Z.; Fan, G.; Guo, Q.; Guo, C.P.; Li, Z.Q.; Zhang, D.; Scripta Materialia, 139(2017) 44-48
CB-8.2:IL05 Impact Tolerant Biocomposites
D. KISAILUS, Materials Science and Engineering, and Department of Chemical and Environmental Engineering, University of California Riverside, CA, USA
Stomatopods are a group of highly aggressive marine crustaceans that strike with high velocity impacts on the heavily mineralized prey on which they feed. Our analysis has revealed that their feeding apparatus (dactyl club) consists of a multi-phase composite with varied material composition and ultrastructures that effect the damage tolerance of this club. We highlight the outer region (termed “impact region”) where we uncover a novel and previously unobserved architectural design, which we call “herringbone structure”, that consists of a compacted and pitch-graded sinusoidal arrangement of helicoidally arranged alpha-chitin/hydroxyapatite fibers and exhibits a notable departure from the traditional helicoidal (Bouligand) structure found within most crustacean exoskeletons. We find this structure, which in combination with an outer dense particulate apatite layer, enhances stress redistribution under compressive loading and yields a tough and impact-resistant structure capable of delivering high-energy strikes without failure. The findings presented herein can provide inspiration and ongoing design guidelines for the fabrication of next-generation impact-resistant composite materials, which are also discussed.
CB-8.2:IL06 Flake Powder Metallurgy: a Bioinspired Pathway to Aluminum Nanocomposites with Nacre-like Structure
ZHIQIANG LI, GENLIAN FAN, ZHANQIU TAN, DINGBANG XIONG, QIANG GUO, YISHI SU, DI ZHANG, Shanghai Jiao Tong University, Shanghai, China
A new strategy of bio-inspired design and fabrication was explored to uniformly distribute nanocarbon in metal matrix composite and coordinate the strength-ductility dilemma. In this report, CNT/Al and GNS/Al composites with reinforcements aligned along the extrusion direction between Al lamellae was fabricated by an approach of flake powder metallurgy, which resorts to make the nanocarbons and metal matrix more compatible both in the surface properties and geometries. Then the nano reinforcement-coated Al nanoflakes were used as building blocks for stack assembly, and then a nacre-like nanolaminate structure could be eventually formed by controlled deformation processing. Compared to the composites of the same reinforcement content but random distribution, the bio-inspired nanolaminate composites exhibited a simultaneous enhancement in tensile strength, Young’s modulus and uniform elongation.
Session CB-8.3 - Bioinspired Functional Surfaces
CB-8.3:IL01 Bioactive and Antimicrobial Biofilm Ceramic Surfaces Synthesized by Advanced Pulsed Laser Technologies
I.N. MIHAILESCU1, C. RISTOSCU1, A. BIGI2, 1National Institute for Lasers, Plasma and Radiation Physics, Magurele, Ilfov, Romania; 2Department of Chemistry “G. Ciamician”, University of Bologna, Bologna, Italy
Basic principles of laser interaction with ceramics and liquids via advanced pulsed laser technologies are introduced and new recent results in synthesis of biomaterial layers are reviewed. Selection by combinatorial pulsed laser deposition of Ag-doped Carbon structures for a new generation of “smart coatings” for orthopaedic, cardiology or dental implants was studied. The best combination with reasonable physical-chemical properties, efficient protection against microbial colonization (Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Enterococcus faecalis and Candida albicans) and beneficial effects on MG63 mammalian cells was found for Ag-doped Carbon films with 2 to 7 at.% Ag. Combinatorial - Matrix-Assisted Pulsed Laser Evaporation was applied to synthesize crystalline gradient thin films with variable composition of Sr-substituted hydroxyapatite and Zolendronate modified hydroxyapatite. The inhibitory action of Zolendronate on osteoclast viability and activity is more efficient than that of Sr, which however plays a greater beneficial role on osteoblast proliferation and viability. C-MAPLE allows to modulate the composition of thin films and hence the promotion of bone growth and the inhibition of bone resorption.
CB-8.3:L02 Flexible and Superhydrophobic Vulcanized Rubber Microstructures
YUJI HIRAI1, RIKU TAMURA1, MASATSUGU SHIMOMURA1, YASUTAKA MATSUO2, TAKAHIRO OKAMATSU3, TOSHIHIKO ARITA4, 1Chitose Institute of Science and Technology, Chitose, Hokkaido, Japan; 2RIES, Hokkaido university, Sapporo, Hokkaido, Japan; 3THE YOKOHAMA RUBBER CO., LTD, Hiratsuka, Kanagawa, Japan; 4IMRAM, Tohoku university, Sendai, Miyagi, Japan
There are various artificial superhydrophobic surfaces that have been reported, however, these are generally brittle and fragile, so that difficult to transform their surface structures. In this study, we have focused on vulcanized rubber, and attempted to prepare flexible and deformable superhydrophobic rubber surfaces by simply vulcanizing pressing with finely patterned Si molds. An unvulcanized rubber sheet containing carbon black, sulfur, and so on, was put on Si molds, which has micron scale hollow array structures prepared by lithographical technique. Then the unvulcanized rubber sheet was pressed and heated at 180 °C for 10 min. After vulcanization, the vulcanized rubber sheet was peeled off from the Si mold. According to the surface observation by a laser microscope, the rubber sheet surface had fine spiky structures, which are inverse structures of the Si mold, and it surface showed superhydrophobicity. Moreover, when microstructured rubber sheet was elongated, their spike-arrangement was transformed from hexagonal to linear without spike height changes, and superhydrophobicity still remained. These results indicate that we can dynamically re-design microstructure arrangements maintaining superhydrophobicity.
CB-8.3:L03 Development and Characterization of Bioinspired Functional Coating on Different Substrates
R. TEJIDO-RASTRILLA, G. BALDI, Colorobbia Consulting s.r.l., Sovigliana, Vinci, Florence, Italy; R. DETSCH, A.R. BOCCACCINI, Institute of Biomaterials, University of Erlangen-Nuremberg, Erlangen, Germany
The outstanding properties of polydopamine (PDA) are known since 2007.PDA is a bioinspired polymer which not only improves the hydrophilicity or the biocompatibility of the surface, but it also offers a platform for post-modification (i.e. grafting of other biomolecules or electroless metal deposition). In addition, PDA is able to bind to virtually all kind of surfaces. In this work, 45S5® Bioglass, novel silicate bioactive glass composition, titanium alloy Ti6Al4V and stainless steel have been functionalized with PDA coating. Moreover, deposition of silver nanoparticles would confer an antibacterial behavior to the samples. In the same way, copper nanoparticles would confer not only an antibacterial behavior, but it would also enhance the angiogenic property of the samples. SEM-EDS results show the successful achievement of both PDA and nanoparticles (both Ag and Cu) deposition on the surface of the samples. In addition, the formation of an hydroxycarbonate apatite-like layer on the bioactive glasses surfaces after soaking them in SBF was confirmed by SEM-EDS and XRD; hence, the presence of the polymer would not interfere with the biomineralization process. Biocompatibility of the samples has been tested and results are very promising, which would confirm the non-toxicity of PDA.
Session CB-8.4 - Bioinspired Materials for Biomedical Applications
CB-8.4:IL01 Multifunctionalized Calcium Phosphates with Anti-resorptive, Anti-Inflammatory and Anti-bacterial Properties
E. BOANINI, Department of Chemistry "Ciamician", University of Bologna, Italy
Among calcium phosphates (CaPs) hydroxyapatite is the most studied and utilized inorganic material for substitution/repair of hard tissues, because of its strong chemical and structural similarity with the inorganic component of bones and teeth. The use of other CaPs such as octacalcium phosphate and alpha tricalciumphosphate, which differ from hydroxyapatite in stoichiometry, structure, morphology and hence in chemical physical properties (i.e. solubility, specific surface area...) is also proposed. The possibility to couple calcium phosphate crystals with drugs or biologically active ions and molecules is a powerful tool to add specific functionalities to bioactive CaPs. In particular, the focus will be held on functionalization with Bisphosphonates, which are widely employed drugs for the treatment of pathologies characterized by excessive bone resorption, and display a great affinity for CaPs; flavonoids such as Quercetin, which displays antioxidant and anti-inflammatory properties; and antibacterial agents such as Silver nanoparticles and monocyclic beta-Lactams. Tailor-made multifunctionalized calcium phosphates may be exploited to provide local release of the functionalizing agents and prevent the drawbacks of systemic treatments.
CB-8.4:IL02 Major Advances in 2D Ceramic Hybrid Materials in Nanomedicine: Challenges and Future Directions
JIN-HO CHOY, Center for Intelligent Nano-Bio Materials (CINBM), Department of Chemistry and Nano Science, Ewha Womans University, Seoul, South Korea
2D-nanoceramic drug delivery systems (2D-NDDS) based on clays have been considered as an important research area not only in bioceramics but also in nanomedicine, since anionic clay such as layered double hydroxide (LDH) was clearly demonstrated as an excellent delivery vehicle with enhanced cellular permeation efficacy. In this presentation, a novel ceramic-biohybrid concept with delivery nanovehicles is proposed to get breakthroughs in 2D-NDDSs. And challenging issues will be discussed along with some experimental findings on ceramic nanovehicles hybridized with therapeutic agents for therapies. More recently, we applied the same strategy to the boron neutron capture therapy (BNCT), since it has long been needed to develop a novel carrier to deliver boron-10 molecules into cells sufficiently. The present inorganic-ceramic hybrids, boron-10-carborate-LDH ones, will be demonstrated in terms of their toxicities, cellular uptake behaviors and neutron capture efficiencies in in-vitro, and their bio-distribution studies in in-vivo. And the future direction with this 2D ceramic strategy will be suggested to build up a new platform technology for 2D-nanoceramic drug delivery systems, which could provide a promising integrative theranostic action in chemo-, gene and radiation therapies.
CB-8.4:L04 Boron Neutron Capture Therapy Assisted by Drug Delivery System
GOEUN CHOI, JIN-HO CHOY, Center for Intelligent Nano-Bio Materials (CINBM), Department of Chemistry and Nano Science, Ewha Womans University, Seoul, South Korea
An attempt was made to apply layered double hydroxide (LDH) as a boron delivery carrier for boron neutron capture therapy (BNCT), which needs a sufficient amount of boron in tumor cells for its successful administration. To meet this requirement, a nanohybrid (BSH-LDH), mercaptoundecahydro-closo-dodecaborate (BSH) anionic molecules in LDH, was developed as a boron delivery system. The cellular boron content upon permeation of BSH-LDH nanoparticles (42.4 μg B/10^6 cells) in U87 glioblastoma cell line was found to be ~ 2000 times larger than the minimum boron requirement (0.02 μg B/10^6 cells) for BNCT, and also orders of magnitude higher than the previous results (0.2 - 1.5 μg B/10^6 cells) by those applied with other targeting strategies, and eventually resulted in excellent neutron capture efficiency even under such low dose (30 μg B/mL) and weak irradiation (1 x 10^12 n/cm^2 corresponding to 20 min) condition. According to the biodistribution studies in xenograft mice model, the tumor-to-blood ratio of BSH in the BSH-LDH-treated-group was found to be 4.4-fold higher than that in the intact BSH treated one in 2 hours after drug treatment. The present BNCT combined with boron delivery system could provide a promising integrative therapeutic platform for cancer treatment.
Session CB-8.5 - Application and Performance of Bioinspired Materials
CB-8.5:IL01 A Highly Sensitive, Reproducible and Uniform SERS Substrate with 3-dimensional Distributed Hotspots of High Density: Gyroid-structured Au Periodic Metallic Materials
DI ZHANG, WANG ZHANG, Department of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai, China
Surface enhanced surface scattering (SERS) has been proved a far important tool in analytic trace detection of many inorganic and organic materials, especially for those involved in medical care, food safety and environment pollution. However, for most of the SERS substrates fabricated by top-down and bottom-up methods, the distribution of hotspots is restricted to one or two dimensions with limited density. Here we report the successful fabrication of a bio-inspired bicontinuous gyroid structured Au SERS substrate with 3D distributed hotspots of high density for the first time. The as-required gyroid structured substrates has been demonstrated to be highly sensitive, reproducible and uniform, with an enhancement factor up to 109. FDTD simulations was conducted to reveal the mechanism for high enhancement, and we found that the interconnected helices in gyroid structure not only increase the density of hotspots, but also contribute to increasing the scattering cross-section of incidence laser. The substrate was then adopted for SERS detection of bis(2-ethylhexyl) phthalate molecules, a most frequently used plasticizer for food, paints, house-hold items, perfume and so on, reaches up to 1fM, which is among the best results ever been reported.