Template-assisted fabrication of nano-biomaterials

“One-dimensional†nanostructures like nanotubes and nanorods hold great potential for a wide variety of applications. In particular, one-dimensional nanostructures may be able to provide many significant advantages over traditional spherical particles for drug delivery applications. Recent studies have shown that long, filamentous particles circulate longer within the body than spherical particles, giving them more time to reach the target area and deliver their payload more efficiently. In addition, studies investigating the diffusion of drugs through nanochannels have shown that the drug diffusion profiles can be controlled by varying the nanochannel diameter when the drug diameter and nanochannel diameter are close in size. The combination of increased circulation time and controllable drug release profiles give onedimensional nanostructure great potential for future drug release applications. To fully realize this potential, a simple, low cost, and versatile fabrication method for one-dimensional nanostructures needs to be developed and exploited. The objective of this work is to demonstrate the versatility of template-assisted nanofabrication methods by fabricating a variety of unique protein and polymer one-dimensional nanostructures. This demonstration includes the adaptation of two different template-assisted methods, namely layer-by-layer assembly and template wetting, to fabricate glucose oxidase nanocapsules with both ends sealed, segmented polystyrene and poly(methyl methacrylate) nanorods, and poly(L-lactide)-poly(methyl methacrylate) core-shell nanowires with adjustable shell layer thicknesses. The unique nanostructure morphologies that were achieved using our novel fabrication methods will open the arena for future research focused on process control and optimization for specific applications

Effect of HNTs addition in the injection moulded thermoplastic polyurethane matrix on the mechanical and thermal properties

The additions of nanofillers are able to enhance the mechanical properties of neat polymer matrix. There were few researchers reported on the mechanical properties of halloysite nanotubes reinforced thermoplastic polyurethane (HNTs-TPU) nanocomposites formed through casting and compression moulding. However, fewer researchers also reported study on HNTs-TPU formed through injection molding. The main objective of this paper was to study the effect of HNTs addition of TPU matrix on mechanical and physical properties. HNTs were mixed in TPU matrix using a brabender mixer with concentration ranging from 0.5 to 7 wt. % HNT loading (at specific mixing speed, mixing time and mixing temperature). Injection moulding was carried out to form tensile bar shaped specimens with specific moulding parameters (injection temperature, injection time and injection pressure). Increment around 35% of tensile strength of the specimen was found at 1 wt. % HNT loading concentration which exhibited the value of 24.3 MPa, compared to neat TPU; the best mixing. The Young’s modulus was increased with increasing HNTs loading. The elongation decreased with increasing HNTs loading. The FESEM results showed that HNTs were dispersed in TPU matrix. The TGA results showed that the addition of 1 wt. % HNTs enhanced the thermal properties. It can be concluded that HNTs-TPU has improved tensile and physical properties compared with neat TPU due to the addition of nanofiller

Mechanism of Nanostructure Formation during Solution Template Wetting

Biomedical research has shown that one-dimensional nanostructures present many potential advantages as delivery vehicles for drugs and biologics. These elongated structures have high aspect ratios that enable increased drug loading capacities and have been shown to have longer in vivo circulation times than other spherical nanoparticles. The increasing interest in these one-dimensional structures has necessitated the developments of fabrication methods for the precise control of the final morphology. A simple, cost effective means of producing nanotubes and nanorods is known as solution template wetting. While this technique has been used to fabricate many different types of elongated nanostructures, the parameters governing the final morphology remain ambiguous. The objectives of this research are to investigate these critical parameters, and furthermore to develop an understanding of the physical mechanism of nanostructure formation. The effects of the infiltration technique, dipping time, polymer molecular weight and template pore size on the morphology of the resulting nanostructure have been evaluated. Key results have established that the infiltration technique is a critical parameter that can enable the formation of stable nanotubes at very low polymer concentrations. Additionally, a tube to rod transition occurs as the infiltration time is increased over 18 hr. An investigation of the rheological properties of high and low molecular weight solutions also indicates that the capillary flow and infiltration of polymer occurs differently. Finally, the pore size was also shown to affect the ability to form hollow, stable structures, and that relatively large pore sizes are necessary for nanotube formation. The culmination of these results is an understanding of the physical layering mechanism of structure formation, and the tube to rod transition can thus be predicted by researchers investigating the use of elongated nanostructures for biomedical applications

Facile Fabrication of Porous Conductive Thermoplastic Polyurethane Nanocomposite Films via Solution Casting

Content of Dataset 1. FTIR spectra 2. Tensile Properties 3. Conductivity 4. Piezoresistive Properties 5. Resistance vs. Strain 6. Porosity Notes : This dataset is linked to Paper: Scientific Reports,2017,DOI: 10.1038/s41598-017-17647-

Nonwoven Mats Based on Segmented Biopolyurethanes Filled with MWCNT Prepared by Solution Blow Spinning

To prepare nonwoven mats constituted by submicrometric fibers of thermally responsive biopolyurethanes (TPU) modified with multiwalled carbon nanotubes (MWCNT), solution blow spinning (SBS) was used. The TPU was the product of synthesis using poly(butylene sebacate)diol, PBSD, ethyl ester L-lysine diisocyanate (LDI), and 1,3-propanediol (PD) (PBSe:LDI:PD) as reactants. TPU was modified by adding different amounts of MWCNT (0, 0.5, 1, 2, and 3 wt.%). The effect of the presence and amount of MWCNT on the morphology and structure of the materials was studied using field-emission scanning electron microscopy (FESEM) and Fourier-transform infrared spectroscopy (FTIR), respectively, while their influence on the thermal and electric behaviors was studied using differential scanning calorimetry (DSC) and capacitance measurements, respectively. The addition of MWCNT by SBS induced morphological changes in the fibrous materials, affecting the relative amount and size of submicrometric fibers and, therefore, the porosity. As the MWCNT content increased, the diameter of the fibers increased and their relative amount with respect to all morphological microfeatures increased, leading to a more compact microstructure with lower porosity. The highly porous fibrous morphology of TPU-based materials achieved by SBS allowed turning a hydrophilic material to a highly hydrophobic one. Percolation of MWCNT was attained between 2 and 3 wt.%, affecting not only the electric properties of the materials but also their thermal behavior.This research was funded by the Fondos de Investigación de Fco. Javier González Benito, política de reinversión de costes generales, Universidad Carlos III de Madrid [2012/00130/004], the Acción Estratégica en Acción Estratégica en Materiales nanocompuestos multifuncionales, Universidad Carlos III de Madrid [2011/00287/003], and the Project PID2020-112713RB-C22–C21 supported by AEI [Ministerio de Ciencia e Innovación of Spain], the University of the Basque Country (UPV/EHU) and (GIU18/216 Research Group)

Fabrication Methods for the Characterization of Nanorods Using Multilayer Polymer Thin Films

Nanoporous templates have seen increased use as a method of creating controlled size nanotubes and nanorods. Currently, the method has focused on the creation of nanomaterials composed of singular polymers or polymer blends. Our study focuses on creating nanomaterials composed of alternating sections of various polymers in a highly controlled manner. The heterostructured, one dimensional polymer nanomaterials may serve for various uses, including biosensors, drug delivery, and biomimetic applications

Nano1D: An accurate Computer Vision model for segmentation and analysis of low-dimensional objects

Microscopy images are usually analyzed qualitatively or manually and there is a need for autonomous quantitative analysis of objects. In this paper, we present a physics-based computational model for accurate segmentation and geometrical analysis of one-dimensional irregular and deformable objects from microscopy images. This model, named Nano1D, has four steps of preprocessing, segmentation, separating overlapped objects and geometrical measurements. The model is tested on Ag nanowires, and successfully segments and analyzes their geometrical characteristics including length, width and distributions. The function of the algorithm is not undermined by the size, number, density, orientation and overlapping of objects in images. The main strength of the model is shown to be its ability to segment and analyze overlapping objects successfully with more than 99% accuracy, while current machine learning and computational models suffer from inaccuracy and inability to segment overlapping objects. Nano1D can analyze one-dimensional (1D) nanoparticles including nanowires, nanotubes, nanorods in addition to other 1D features of microstructures like microcracks, dislocations etc

Shape memory polymeric nanocompsites for biological applications

The aim of this work is to develop novel shape memory polymers (SMPs) and nanocomposites for potential biological applications. A kind of commercial SMP, shape memory polyurethane (SMPU), was used to prepare nanocomposites by incorporating nano-clay into the SMPU substrate. The mechanical behaviour, thermal property and shape memory efficiency were studied with various nanofiller loadings. Chemical synthesis methods were also employed to prepare the other designable SMP and its nanocomposites, i.e. the shape memory polystyrene co-polymer (SMPS). Multiple technologies were adopted to enhance the SMPS matrix such as modifying the chemical components, introducing various functional nanoparticles into the polymeric network and improving the dispersion of the nanoparticles. Different methods were used to characterize the overall performance of the obtained materials. Mechanical tests were performed at different dimensional scales with a varied degree of localisation. Nanoindentation was firstly applied to assess the micro-mechanical properties of shape memory polymer nanocomposites at scales down to particle size. The micro-mechanical analysis provided the fundamental information on the SMPs and their nanocomposites for bio-MEMS applications. Potential applications were also explored through manufacturing different type of device models and testing their shape recovery efficiencies. Finally, theoretical contributions were made in two areas. The first one was the theoretical analysis on the nanoparticles enhancement to the soft polymeric matrix. The other was in developing a constitutive model to describe the thermo-viscoelastic property and shape memory behaviour for SMP nanocomposites

Synthesis of Polyhedral Oligomeric Silsesquioxane (POSS) Functionalized Carbon Nanotubes for Improved Dispersion in Polyurethane Films

Carbon nanotube (CNT) polymer nanocomposites are promising advanced materials. These materials exhibit the advantages of traditional polymeric materials, such as being light weight and easy to process, combined with the potential to exhibit enhanced mechanical, thermal and electrical properties compared to pure polymers. To achieve substantial improvement of composite properties at low CNT loading, uniform dispersion of CNTs in the polymer matrix and strong CNT-polymer interfacial interaction are needed. However, it is difficult to achieve adequate dispersion and interfacial interactions due to the inert nature of CNTs. In this project, polyhedral oligomeric silsequioxane (POSS) will be used as a dispersing agent for multi-walled carbon nanotubes (MWNTs) in polyurethane (PU) matrices. This dissertation consists of six chapters. Chapter I provides a detailed introduction of the fundamental knowledge of CNTs, PU, and POSS. At the end of this chapter, the motivation and rationale of this research are given. Chapter II establishes the overall goal and specific objectives of this research. Chapter III describes the synthesis and characterization of three POSS modified CNTs and one organosilane modified CNT. Grafting efficiency of the different grafted molecules are calculated and compared. Chapter IV discusses the dispersion behavior of four covalently modified CNTs in both solvents and PU matrices. Differences in dispersion behaviors of the modified CNTs are correlated to the solubility parameters of the grafting molecules and the surface structures of modified CNTs. Chapter V provides further discussion of the dispersion of POSS and silane modified CNTs by reviewing the assessment of the physical properties of PU composites containing the modified CNTs. Morphological, thermal, mechanical and electrical properties are used to estimate the interactions of the modified CNTs with the PU matrix. Chapter VI explores the function of the trisilanolphenyl POSS lithium salt (TSPLi) as a dispersant for CNTs in thermoplastic polyurethane (TPU) during melt extrusion. The dispersion of CNTs and TSPLi modified CNTs are estimated by mechanical and electrical property measurement of the PU/CNT and PU/CNT-POSS composites

신축성 있고 착용 가능한 탄소 나노튜브 기반 전자 기술

학위논문 (박사) -- 서울대학교 대학원 : 공과대학 협동과정 바이오엔지니어링전공, 2020. 8. 김대형.Networks of carbon nanotubes (CNTs) are a promising candidate for use as a basic building block for next-generation soft electronics, owing to their superior mechanical and electrical properties, chemical stability, and low production cost. In particular, the CNTs, which are produced as a mixture of metallic and semiconducting CNTs via chemical vapor deposition, can be sorted according to their electronic types, which makes them useful for specific purposes: semiconducting CNTs can be employed as channel materials in transistor-based applications and metallic CNTs as electrodes. However, the development of CNT-based electronics for soft applications is still at its infant stage, mainly limited by the lack of solid technologies for developing high-performance deformable devices whose electrical performances are comparable to those fabricated using conventional inorganic materials. In this regard, soft CNT electronics with high mechanical stability and electrical performances have been pursued. First, wearable nonvolatile memory modules and logic gates were fabricated by employing networks of semiconducting CNTs as the channel materials, with strain-tolerant device designs for high mechanical stability. The fabricated devices exhibited low operation voltages, high device-to-device uniformity, on/off ratios, and on-current density, while maintaining its performance during ~30% stretching after being mounted on the human skin. In addition, various functional logic gates verified the fidelity of the reported technology, and successful fabrication of non-volatile memory modules with wearable features has been reported for the first time at the time of publication. Second, the networks of semiconducting CNTs were used to fabricate signal amplifiers with a high gain of ~80, which were then used to amplify electrocardiogram (ECG) signals measured using a wearable sensor. At the same time, color-tunable organic light-emitting diodes (CTOLEDs) were developed based on ultra-thin charge blocking layer that controlled the flow of excitons during different voltage regimes. Together, they were integrated to construct a health monitoring platform whereby real-time ECG signals could be detected while simultaneously notifying its user of the ECG status via color changes of the wearable CTOLEDs. Third, intrinsically stretchable CNT transistors were developed, which was enabled by the developments of thickness controllable, vacuum-deposited stretchable dielectric layer and vacuum-deposited metal thin films. Previous works employed strain-tolerant device designs which are based on the use of filamentary serpentine-shaped interconnections, which severely sacrifice the device density. The developed stretchable dielectric, compatible with the current vacuum-based microfabrication technology, exhibited excellent insulating properties even for nanometer-range thicknesses, thereby enabling significant electrical performance improvements such as low operation voltage and high device uniformity/reproducibility, which has not been realized in the most advanced intrinsically stretchable transistors of today.탄소 나노튜브는 뛰어난 전기적, 화학적, 그리고 기계적 특성을 갖고 있어 차세대 유연 전자소자의 핵심 소재 중 하나로 각광을 받고 있으나, 아직까지 이를 이용한 실용적인 유연 전자소자의 개발은 실현되지 않고 있다. 이는 탄소 나노튜브의 전기적 특성대로 완벽히 분류해 낼 수 있는 기술, 탄소 나노튜브를 소자의 원하는 위치에 정확히 원하는 양만큼 네트워크 형태 혹은 정렬된 형태로 증착하는 기술, 그리고 유연 전자소자를 구성하는 다른 물질들의 개발 기술의 부재 때문이다. 지난 10여년간 해당 기술들은 광범위하게 연구되어지고 있으나, 탄소 나노튜브를 활용한 우수한 유연 전자소자 개발을 위한 핵심 기술들의 발전은 아직 초기 단계에 있다. 따라서 이 논문을 통해 탄소 나노튜브를 유연 전자소자에 적용시킬 수 있는 새로운 기술을 소개하고자 한다. 첫번째로 탄소 나노튜브와 유연 전자소자의 소자 디자인을 이용하여 피부위에 증착 가능한 비휘발성 메모리 소자를 제작하였고, 해당 기술을 이용하여 피부위에서 안전하게 동작할 수 있는 다양한 기초 회로들을 구현하였다. 탄소 나노튜브 기반 메모리 전자 소자 및 회로는 다양한 외부 응력이 가해져도 안정적으로 동작을 하였고, 개발된 기술을 통해 보다 실용적인 탄소 나노튜브 기반 유연 전자 소자의 제작 조건을 확립할 수 있었다. 두번째로 위에 개발된 기술을 바탕으로, 보다 복잡한 탄소 나노튜브 기반 유연 회로 및 구동전압에 따라 발광색이 변환하는 색변환 소자를 제작하여 해당 소자들이 피부위에 부착되어 잘 작동되도록 구현하였다. 그리고 이 두 가지 웨어러블 전자소자를 통합하여 실시간으로 심전도를 측정하여 탄소 나노튜브 기반 전자소자를 통해 해당 신호를 증폭시키고, 신호의 상태를 색변환 소자로 나타낼 수 있는 심전도 모니터 시스템을 구현하였다. 세번째로 진공 증착이 가능한 유연 절연체를 개발하여, 기존의 유연 전자소자들이 가지고 있던 극명한 한계를 극복하였다 (높은 구동 전압, 낮은 집적도, 대면적 소자 선능 균일도 등). 기존의 액상 기반 증착을 위주로 한 유연 전자 소자들은 무기물질 기반 전자소자 대비 극심한 성능 저하를 보여주었는데, 이를 해결하기 위해 새로운 절연물질을 개발하고 탄소 나노튜브 기반 유연 전자소자에 적용하여 그 가능성을 보여주었다.Chapter 1. Introduction 1 1.1 Discovery of CNTs and their benefits for soft electronic applications 1 1.2 Electrical sorting of CNTs 5 1.3 Deposition methods of solution-processed semiconducting CNTs 7 1.4 Conclusion 23 1.5 References 24 Chapter 2. Stretchable Carbon Nanotube Charge-Trap Floating-Gate Memory and Logic Devices for Wearable Electronics 32 2.1 Introduction 32 2.2 Experimental section 34 2.3 Results and discussion 36 2.4 Conclusion 62 2.5 References 63 Chapter 3. Wearable Electrocardiogram Monitor Using Carbon Nanotube Electronics and Color-Tunable Organic Light-Emitting Diodes 67 3.1 Introduction 67 3.2 Experimental section 70 3.3 Results and discussion 73 3.4 Conclusion 97 3.5 References 98 Chapter 4. Medium-Scale Electronic Skin Based on Carbon Nanotube Transistors with Vacuum-Deposited Stretchable Dielectric Film 102 4.1 Introduction 102 4.2 Experimental section 106 4.3 Result and discussion 111 4.4 Conclusion 135 4.5 References 136Docto