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1 Establishment of a Thematic Unit of Excellence (TUE) at IIT Kanpur Soft Nanofabrication and Nanofabrication with Soft Matter: with Applications in Energy, Environment and Bio-platforms

2 Nanofabrication with Soft Matter & Use Ashutosh Sharma Sri Sivakumar Prashant Bhattacharya Nishith Verma Animangsu Ghatak (Chemical Engineering) Aswani Thakur (Biological Sciences and Bioengineering) Sandeep Verma (Chemistry) Ashish Garg Bikramjit Basu Vivek Verma (Materials Engineering) Shantanu Bhattacharya (Mechanical Engineering) Krishnacharya (Physics)

3 Understanding Fabrication/Manufacturing Use of Small scale structures In Soft materials & using Soft routes

4 MAJOR OBJECTIVES (A) State-of-the-art the art facility and resources for research and development activities in the areas of soft nanofabrication. (B) New methods and creative combinations of top-down and bottom- up, wet and dry and soft and hard to push the boundaries of sub-100 nmfabricationwithanemphasisonmulti-scale materials and devices in the context t of energy, environment and biological applications. (C) Applications of soft nanofabrication routes to fabrication of devices and structures in other final materials of use such as ceramics and carbon. (D) Collaborations and training with other institutions & corporate R&Ds in this emerging g area, thereby creating an expert base which does not currently exist in our country.

5 Themes Self-organized nano-fabrication in soft materials New and creative combinations of top-down and bottom-up for large area functional interfaces for control of wetting, adhesion, friction, optical, recognition, properties. Nano- mechanics of soft confined materials Stability of soft nanostructures DNA fractionation using surface electrophoresis on nano-patterned surfaces responsive surfaces with tunable nanopatterns

6 Functional carbon multiscale structures from polymers: MEMS to NEMS; remediation to batteries Micro/nano carbon capsules for actives delivery, imaging, g synthesis of high temp nanoparticles Mesoporous carbon based; Functional porous electrospun nanofibers: for environment, health and energy applications Nanostructured organic solar cells Nanocomposites: polymer, carbon, metal, oxides. cell-material interaction on nanotextured polymer and carbon bioactive surfaces

7 Lanthanide-doped nanomaterials in solid state lighting & solar cells. carbon nano-tube/cnf based dry adhesives Protein aggregate based nanomaterials & surfaces: Peptide self-assembling nano-structures

8 Large surface areas, rapid nano-patterning of soft interfaces & films by self-organization: Functional interfaces for control of wetting, adhesion, friction, optical properties 1. Controlled dewetting on physically and chemically heterogeneous surfaces: Miniaturization of length scales 2. Electric field as a tool of nanofabrication 3. Ultrafast micro-patterning of polymeric and metal films using laser irradiation 4. Patterning in soft solid-state: elastic instabilities 5. Nanophase seperation 2 µm 98 nm 2.0µm 78 nm 78 nm 500 nm

9 Example: Fabrication of responsive surfaces with tunable nano-roughness and study of the wetting/adhesion/friction transitions. Key aspects of the methodology Fabricating surfaces with dual scale roughness. Fabrication of first generation roughness by topographic substrates with different patterns (rectangular and triangular array of pillars) of varying height, width and periodicity (from hundreds of micron to tens of nanometer). Fabrication of second generation roughness by grafting thermo-responsive polymer brushes (poly-n-isopropylacrylamide l l (PNIPAAm)). Vary the temperature around lower critical solution temperature (LCST ~ 32 0 C) of PNIPAAm to tune the nano-roughness. Study the wetting transitions and its dynamics.

10 Poly(N-isopropylacrylamide) (PNIPAAm) (LCST ~ 32 0 C) Behavior of PNIPAAm polymer brushes below and above the LCST; showing brush like and bundled d structures t resulting in different nano-roughness depicting different wetting morphologies. T ~ 25 o C T > 40 o C θ = 63.5 o θ = 93.2 o θ = 86.6 o θ = o Wettability characterization of a Wettability characterization of a polished silicon substrate grafted with rough (sand blasted) silicon PNIPAAm substrate grafted with PNIPAAm T. Sun et al. Angew. Chem. Int. Ed. 43, 357 (2004)

11 Example: Surface Electrophoresis of ds-dna on nanopatterned surfaces 1. Fabrication of nanopatterned topographies and hydrophilic and hydrophobic patterns on PDMS and other Polymeric surfaces. 2. Understanding of the DNA mobility and fractionation due to patterned surfaces. 3. Fabrication of a device to monitor real time data on molecular motion. 4. To develop a model by the help of the Molecular dynamic simulations for the interaction between pattern surfaces and molecules.

12 Nanostructured surfaces SEM image of a Teflon surface doped with SiC Nanoparticles

13 Example: Directed self-assembly on nanopatterned surfaces: Patterning of proteins at nanoscale using Biotin-Avidin Use of nanoscale neutravidin templates for directed self assembly of biotinylated molecules esp. proteins Biotin-avidin bond is strongest non-covalent bond (Ka ~ M -1 ) known to biochemists Biotin-avidin idi bond used extensively in immunoassays, flow cytometry, affinity chromatography etc. Versatile technique: Any biotinylated protein could be immobilized specifically precisely in nanoscale regime. Will help in: Manipulation of proteins at nanoscale to understand cell division Developing protein arrays for sensing

14 Directed self assembly Biotinylated cellulose was bound to the microtubules via biotin- neutravidin link Manipulation of proteins at nanoscale Microtubules and kinesin proteins linked using biotinavidin and allowed to self organize on surface Studied time dependent growth dynamics of microtubules Patterning of microtubule seeds at specific Overlapping of locations desirable proteins and cellulose Scale bars: 10 μm t = 10 t = 40 t = 130 min

15 Spin coat resist Methodology Resist Glass Partially expose resist (UV or ebeam) Develop resist Incubate neutravidin Strip neutravidin Flow biotinylated protein Scale bar: 10 µm Neutravidin patterns on glass slide via photo-lithography Biotinylated proteins, microtubules e.g., can be immobilized on patterned neutravidin via directed self assembly Microtubule dynamics studies can help manipulate cell division in cancer cells

16 Fabrication of Multiscale Carbon-structures from C-MEMS to C-NEMS Carbon micro-nano multiscale structures and nanocomposites with controlled porosity in the form of devices, wires, networks, scaffolds, particles, fibers, films..are required for sensors, micro-battery electrode arrays, bio- MEMS, supercapacitors, bioplatforms, nanoreactors, active delivery

17 CARBON cannot be easily and inexpensively shaped on micro and nanoscales over large areas by the current silicon technology (FIB, E-beam, photolithography..) We propose fabricating meso-structures in an appropriate precursor polymer and then pyrolize The meso-structures will be hierarchal (10 nm to 100 micron scales) and fractal to maximize transport & surface area and minimize transfer losses Novel combination of top-down and self-organization to fabricate precursor polymeric micro- and nanostructures Control of carbon properties Creation of hierarchal and fractal carbon structures (maximize transport & surface area)

18 Example: Biocompatibility of Nano patterned and nanofibrous scaffolds Different Surface Features UV, Oxygen Plasma Treatment t Random, Aligned Hydrophobic, Hydrophilic

19 Electrospinning 200n m Process parameters Electric field; Viscosity/flow rate; Material parameters Distance between nozzle and Fiber orientation collector Fiber size Fibers 104 Thin Film 80 Fiber composition Surface wettability

20 Lanthanide-doped or coated or imbedded nanoparticles White light through up-conversion; solar cells White light through up conversion; solar cells NIR light Matrix:Yb 3+ /Tm 3+ /Er 3+

21 Porous and Hollow Polymeric and Carbon particles: For growth of high temperature nano-materials, actives delivery and imaging

22 Catalytic Micro-Nano Hierarchal Webs and Composites of Activated Carbon: Platforms for control of gaseous and aqueous phase systems; high area electrodes; filters Objectives: Synthesis of metals incorporated polymeric nanofibers, nanobeads & porous gels; carbonization and activation; growth of carbon nano-fibers (CNF) within the macro-pores by chemical vapor deposition (CVD), electrospining. i Characterization of hierarchal micro/nano porous structures by by various techniques, including SEM/XRD/TGA/DSC/BET and pore-size distribution (PSD) analyzers. Adsorbents and catalysts for the control of contaminants such as volatile organic compounds (VOC) andsox/nox in air, and arsenic and fluoride ions in wastewater. t The materials mayalso be used as adsorbents for the removal of bioactive substances such as amino acids and Vitamin B-12 from process fluids.

23 Objectives: Biotic Abiotic Interface at the Nanoscale Identification and synthesis of metal binding peptide segments Introduction of functionalities supporting metallization reaction Metalization and peptide immobilization on surfaces Detection of metal ion driven conformational changes Approach: Scheme 1. Self assembly of triple bond containing peptide fragments (synthesis), click reaction, and metallization (abiotic label). Sandeep Verma

24 Metalized peptide/protein fibers: Microscopy Assembly mechanisms Material aspects Detect changes in conformation Sandeep Verma

25 Fabrication of protein aggregate based nanomaterials & surfaces: Some applications of proteins in soft material formation Self assembling peptide nanofiber scaffold for 3-D cell cultures Insulin fibers for sustained treatment of type 1 diabetes mellitus Plos One 2006 Dec 27 Proc Natl Acad Sci U S A. 2010

26 Peptide/ protein design, synthesis/expression, purification and characterization Solid phase peptide synthesis Recombinant techniques Chromatography and mass spectrometry Basic self assembly of protein nanofiber formation: Monitoring of self assembling process Chromatography based assays Fluorescence based assays Characterization acte at of nanofibers TEM, SEM, AFM Circular dichriosm, FT-IR Dynamic light scattering Engineered nanomaterials and scaffolds for tissue engineering applications Curlin, chaplins, polyglutamine sequences Supramolecular biopharmaceuticals Therapeutic monoclonal antibodies Growth factors

27 Budget No Item Budget Total (in Rupees) 1 st Year 2 nd Year 3 rd Year 4 th Year 5 th year A Recurring 1 Salaries/wages 31,56,000 33,19,200 34,82,400 36,45,600 38,08,800 1,74,12,000 2 Consumables 25,00, ,00, ,00, ,00, ,00, ,25,00,000 3 Travel 2,50,000 2,50,000 2,50,000 2,50,000 2,50,000 10,00,000 4 Contingencies & Maintenance* 25,00,000 25,00,000 25,00,000 25,00,000 25,00,000 1,25,00,000 B Equipment 8,52,00,000 8,52,00,000 Grand Total 8,69,00,000 85,69,200 87,32,400 88,95,400 90,58,800 12,46, 56,000 Overheads DST norms Total

28 Budget for man power Designation & number of persons Monthly Emoluments (including 30% HRA) Sr. Project Scientist (2) Rs. 30,000 per month with Rs yearly increments Project Scientist (6) Rs. 20,000 per month with Rs yearly increments Sr. Project associate/project associate (5) Rs. 15,000 per month with Rs. 800 yearly increments Project Technician (1) Rs per month Budget 1 st Year 2 nd Year 3 rd Year 4 th Year 5 th year Total (in Rupees) 7,20,000 7,63,200 8,06,400 8,49,600 8,92,800 40,32,000 14,40,000 15,12,000 15,84,000 16,56,000 17,28,000 79,20,000 9,00,000 9,48,000 9,96,000 10,44,000 10,92,000 49,80,000 96,000 96,000 96,000 96,000 96,000 4,80,000 Total 31,56,000 33,19,200 34,82,400 36,45,600 38,08,800 1,74,12,000 Total 1,74,12,000

29 Budget for equipment S. Generic name of the equipment along Imported/ Estimated Spare time for No with make and model indigenous Costs (in other users (in Rupees %) (INR)) 1 Confocal laser scanning microscope Imported 100,00, % with UV and NIR Laser 2 Nanomanipulator nanowork station Imported 100,00,000 30% 3 Maskless Lithography with 1 micron resolution Imported 80,00,000 40% 4 Laser patterning tool Imported 60,00,000 30% 5 Furnace for high temp pyrolysis (~ 1800 o C-3000 o C) Imported 65,00,000 30% 6 AFM with electrical and magnetic Imported 40,00,000 20% properties mapping 7 TGA/DSC Imported 35,00,000 40% 8 Flow cytometry Imported 25,00, % 9 Nanoparticle viewing unit: Imported 20,00,000 20% 10 Wettability contact angle goniometer imported 25,00,000 30% 11 Reflection mode attachment for Imported 12,00, % existing near field and Micro-Raman setup

30 Budget for equipment S. No Generic name of the equipment Imported/ind Estimated Spare time for along with make and model igenous Costs (in other users Rupees (in %) (INR)) 12 Laser for raman 532 nm Imported 14,00,000 For Raman; 0% 13 Laser Nano Particle Size Analyzer Imported 20,00,000 50% 14 Stylus Profilometry Imported 15,00,000 40% 15 High speed cameras (3) Imported 20,00,000 50% 16 High speed low intensity camera for Imported 15,00,000 30% cell tracking 17 Protein purification system Imported 20,00,000 20% 18 Fuel Cell Test Kit Imported 37,00, % Electron probe microanalyzer Imported 15,00,000 For SEM 19 FTIR Imported 10,00,000 40% 20 Furnaces (2 numbers) for low temp Imported 20,00,000, 20% pyrolysis (~ 1200 C) 21 High power UV/Plasma chambers with Sources (2) Imported 10,00,000 20% 22 Gel Doc Imported 8,00, % 23 Fluorescence attachment Imported 8,00,000 25%

31 Budget for equipment S. No Generic name of the Imported/indigenous Estimated Spare time for equipment along with Costs (in other users make and model Rupees (in %) (INR)) 24 Dip Coater, hot plate, Imported 6,00,000 00% glove box, vortexers, centrifuges, dispensing pipettes, electrophoresis benches 25 UV collimated source Imported 5,00,000 20% 26 E-beam evaporation attachment Imported 5,00,000 20% 27 Deep freezer Imported 5,00, % 28 PCR Imported 3,00,000 30% 29 Milipore water purification system Imported 3,00,000 25% 30 CCD cameras for existing Imported 4,00,000 30% microscopes (2) 31 Weighing balance Imported 1,00,000 00% 32 Vibration isolation table Imported ,50,000 00% 33 Vibration generator Imported 50,000 00%

32 Budget for equipment S. No Generic name of the equipment along with make and model 34 load cell, amplifier and Data acquisition system Imported/indigenous Estimated Costs (in Rupees (INR)) Spare time for other users (in %) Imported 3,00,000 00% 36 Nano-positioner Imported ,00,000 25% 37 Electroluminescence Imported 3,00,000 40% attachment 38 Mass flow controller Imported 3,00,000 00% 39 Cell counter for cell Imported 3,00,000 20% viability 40 Thin film deposition unit Imported 4,00,000 25% 41 Bench top Mini lathe Imported 6,00, % 42 Wire bonder Imported 9,00,000 Total 8,52,00,000

33 Prof. Ajay K. Sood National Advisory Committee: Prof. G. Sundarrajan Prof. Arup K. Raychaudhuri Prof. Dipankar D. Sarma Prof. Milan K. Sanyal

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