Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

面向可视化纳米操作的DNA分子运动学建模研究

利用原子力显微镜(AFM:Atomic Force Microscopy)对DNA进行单分子纳米操作对生命科学的发展具有特别重要的意义,但是AFM纳米操作缺乏实时视觉反馈的问题依然制约着生物操纵技术的发展.虚拟现实技术是解决该问题的有效方法之一,但是必须预先建立起被操作物体的运动学模型.目前面向可视化纳米操作的建模研究多针对纳米棒、纳米颗粒等刚性物体展开,很少涉及到柔性DNA分子的运动建模方法。针对该问题,本文以弹簧-质点模型为基础,借鉴统计力学在DNA机械特性上的研究成果,提出了一种具有较强物理意义和实际可信度的柔性DNA分子运动学建模方法,并进行了相关仿真实验研究,从而为实现DNA分子的可视化纳米操作提供了理论依据。

机器人化纳米操作中任务空间的实时反馈方法研究

纳米科技的最终目标是在原子、分子尺度上，制造具有新颖物理、化学和生物特性的器件和系统，而实现这个目标最为关键的使能技术便是纳米尺度下进行观测、操作和装配的科学方法与相关技术手段。原子力显微镜（AFM：Atomic Force Microscopy）的发明为实现这一目标提供了可行途径，AFM除了能够在常态下实现对原子、分子尺度大小物体的观测，并且由于其超高的分辨率和运动精度，可控、可重复的运动方式，独特的机械力作用机理，任意环境的可适应性而广泛应用于纳米操作。然而AFM的主要功能是进行纳米观测，应用于纳米操作时面临着许多挑战性的难题，尽管随着近十年的深入研究，一些问题已经得到了部分解决，但是缺乏高可信度的实时视觉反馈、无法实现任务空间内探针的精确定位依然阻碍着AFM纳米操作的效率。以目前最为先进的AFM纳米操作方法—增强现实技术为例，尽管该技术可以为操作者提供实时的视觉反馈，但是这种视觉反馈并不代表纳米操作场景的真实变化，而是根据离线模型计算得到的一种图形仿真，因而视觉反馈是否可信取决于模型的准确程度，然而受纳米尺度下各种非线性力的影响，如毛细力、范德华力、静电力等等，很难建立完全精确的物理模型，模型误差将导致错误的视觉反馈并引起纳米操作的失败。此外，受PZT非线性和温漂的影响，基于AFM的纳米操作还缺乏在任务空间内对探针进行精确定位的能力，导致操作过程中AFM探针无法有效接触到纳米物体，使得机器人学中“从A点运动到B点”最为基本的任务难以实现，这些缺点都严重阻碍着AFM纳米操作的效率和效果。本论文针对上述问题，以机器人学中的感知、决策、行为理论和监控方法为基础，具体开展了以下几方面的工作： 1、视觉反馈缺乏可信度是基于增强现实AFM纳米操作面临的主要问题，由于操作者无法对视觉反馈可信度作出评断，经常会在错误视觉反馈的指引下进行无效的纳米操作，从而浪费大量的时间，降低了AFM纳米操作的效率。为了克服上述问题，本文在研究信息诊断与反馈理论基础上，提出了基于Kalman滤波的视觉反馈可信度在线监控方法，实现了视觉反馈错误的实时检测，避免了无效纳米操作的发生，提高了AFM纳米操作的效率。 2、错误视觉反馈被检测出后，需要对其修正以保证纳米操作任务的成功完成。然而传统修正方法需要中断纳米操作进行重新扫描成像，这往往需要耗费几分钟的时间，严重降低了AFM纳米操作的效率。针对该问题，本文提出一种基于局部扫描的在线修正方法，通过扫描轨迹的优化，该方法能够对真实纳米操作结果进行实时感知，从而不需要中断纳米操作就能实现错误视觉反馈的修正，并使得整个修正过程对于操作者透明。这保证了实时可视监控信息的真实性，显著提升了AFM纳米操作的效率。 3、PZT非线性和随机漂移是影响AFM探针精确定位的主要因素，针对该问题本文提出了一种基于路标的探针定位方法，其核心思想是不再采用距离为测度方式进行探针位置描述，而是将作业区域的特定形貌特征定义为参考路标，通过探针对特征形貌的主动感知实现基于路标地图的探针定位，有效消除PZT非线性和随机漂移引起的定位误差，提高探针在任务空间内的定位精度。 4、研究了机器人化纳米操作系统任务空间实时反馈的构建技术，具体包括高灵敏度纳米操作力的感知方法，系统结构误差的产生原因和补偿策略，面向探针实时运动控制的系统结构设计，系统的软硬件实现方案等内容，并利用该实验平台开展了大量实验研究，验证了本论文所提出理论方法的正确性，同时演示性地组建了基于单根CNT和DNA的纳电子器件，实验结果表明AFM纳米操作的效率和效果得到了极大提升。本文的研究工作丰富了基于AFM的机器人化纳米操作理论，为基于AFM的纳米制造技术发展提供了具有一定指导意义的理论方法和研究途径。

Production of carbon nanotubes by PECVD and their applications to supercapacitors

Màster en Nanociència i Nanotecnologia

Preparation, characterization and evaluation of drug-delivery systems: Pectin and mefenamic acid films

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Polimeri biocompatibili come substrati per colture cellulari

Questo lavoro costituisce un'interfaccia tra la fisica dei materiali e la biologia; sfruttando le particolari proprietà del polimero conduttore poli(3,4-etilenediossitiofene) drogato con poli(stirene sulfonato) (PSS), o PEDOT:PSS, sono stati sviluppati e realizzati substrati per colture cellulari. Tale composto è infatti un polimero organico biocompatibile, caratterizzato da proprietà fisiche che ben si prestano ad applicazioni in campo biologico. Vengono inizialmente descritte le caratteristiche generali e gli schemi di classificazione dei polimeri, per analizzare quindi in dettaglio i polimeri conduttori e la loro modalità di drogaggio. Si presenta quindi il PEDOT:PSS, del quale vengono descritte le proprietà, in particolare ci si sofferma sulle quelle termiche, meccaniche ed elettriche. Il primo capitolo si conclude con la presentazione delle applicazioni bioelettroniche del PEDOT:PSS, illustrando le principali applicazioni nella ricerca biologica e descrivendo le caratteristiche che ne hanno fatto uno dei composti più utilizzati per questo tipo di applicazioni. Nel secondo capitolo, per la parte sperimentale, sono stati descritti approfonditamente gli strumenti e i materiali utilizzati; in particolare vengono spiegati dettagliatamente il procedimento di spin-coating per la produzione di film sottili e le tecniche AFM (Atomic Force Microscopy) per l'analisi della morfologia superficiale. Nel terzo capitolo vengono esposte le tecniche sperimentali impiegate: è stata sviluppata una procedura di produzione ripetibile, grazie alla quale sono stati realizzati dei campioni, per i quali poi è stata misurata la rugosità. I risultati conseguiti sono stati infine correlati con l'analisi della proliferazione cellulare, illustrata chiaramente dalle immagini ottenute al microscopio ottico, che rivelano l'adesione e la moltiplicazione cellulare sui substrati di PEDOT:PSS.

Caratterizzazione della superficie di array di nanofili di silicio

Nel primo capitolo viene introdotto lo studio eff�ettuato e descritto un metodo di misure successivo alla caratterizzazione della super�ficie. Nel secondo capitolo vengono descritti i campioni analizzati e, nello speci�fico, la crescita attraverso MaCE dei nanofi�li di silicio. Nel terzo capitolo viene descritto lo strumento AFM utilizzato e la teoria della caratterizzazione alla base dello studio condotto. Nella quarta sezione vengono descritti i risultati ottenuti mentre nelle conclusioni viene tratto il risultato dei valori ottenuti di RMS roughness e roughness exponent.

Immobilization and characterization of recombinant esterase enzyme on chitosan nanoparticles

Immobilization of biologically important molecules on myriad nano-sized materials has attracted great attention. Through this study, thermophilic esterase enzyme was obtained using recombinant DNA technology and purified applying one-step His-Select HF nickel affinity gel. The synthesis of chitosan was achieved from chitin by deacetylation process and degree of deacetylation was calculated as 89% by elemental analysis. Chitosan nanoparticles were prepared based on the ionic gelation of chitosan with tripolyphosphate anions. The physicochemical properties of the chitosan and chitosan nanoparticles were determined by several methods including SEM (Scanning Electron Microscopy), FT-IR (Fourier Transform Infrared Spectroscopy) and DLS (Dynamic Light Scattering). The morphology of chitosan nanoparticles was spherical and the nanospheres’ average diameter was 75.3 nm. The purified recombinant esterase was immobilized efficiently by physical adsorption onto chitosan nanoparticles and effects of various immobilization conditions were investigated in details to develope highly cost-effective esterase as a biocatalyst to be utilized in biotechnological purposes. The optimal conditions of immobilization were determined as follows; 1.0 mg/mL of recombinant esterase was immobilized on 1.5 mg chitosan nanoparticles for 30 min at 60°C, pH 7.0 under 100 rpm stirring speed. Under optimized conditions, immobilized recombinant esterase activity yield was 88.5%. The physicochemical characterization of enzyme immobilized chitosan nanoparticles was analyzed by SEM, FT-IR and AFM (Atomic Force Microscopy).

Investigating The Fate Of Positively Charged Nanoparticles In A Soil Environment

The recent increase in the amount of nanoparticles incorporated into commercial products is accompanied by a rising concern of the fate of these nanoparticles. Once released into the environment, it is inevitable that the nanoparticles will come into contact with the soil, introducing them to various routes of environmental contamination. One route that was explored in this research was the interaction between nanoparticles and clay minerals. In order to better define the interactions between clay minerals and positively charged nanoparticles, in situ atomic force microscopy (AFM) was utilized. In situ AFM experiments allowed interactions between clay minerals and positively charged nanoparticles to be observed in real time. The preliminary results demonstrated that in situ AFM was a reliable technique for studying the interactions between clay minerals and positively charged nanoparticles and showed that the nanoparticles affected the swelling (height) of the clay quasi-crystals upon exposure. The preliminary AFM data were complemented by batch study experiments which measured the absorbance of the nanoparticle filtrate after introduction to clay minerals in an effort to better determine the mobility of the positively charged nanoparticles in an environment with significant clay contribution. The results of the batch study indicated that the interactions between clay minerals and positively charged nanoparticles were size dependent and that the interactions of the different size nanoparticles with the clay may be occurring to different degrees. The degree to which the different size nanoparticles were interacting with the clay was further probed using FTIR (Fourier transform infrared) spectroscopy experiments. The results of these experiments showed that interactions between clay minerals and positively charged nanoparticles were size dependent as indicated by a change in the FTIR spectra of the nanoparticles upon introduction to clay.

Impact of N2 plasma power and duration on AlGaN/GaN HEMT

urface treatments have been recently shown to play an active role in electrical characteristics in AlGaN/GaN HEMTs, in particular during the passivation processing [1-4]. However, the responsible mechanisms are partially unknown and further studies are demanding. The effects of power and time N2 plasma pre-treatment prior to SiN deposition using PE-CVD (plasma enhanced chemical vapour deposition) on GaN and AlGaN/GaN HEMT have been investigated. The low power (60 W) plasma pre-treatment was found to improve the electronic characteristics in GaN based HEMT devices, independently of the time duration up to 20 min. In contrast, high power (150 and 210 W) plasma pretreatment showed detrimental effects in the electronic properties (Fig. 1), increasing the sheet resistance of the 2DEG, decreasing the 2DEG charge density in AlGaN/GaN HEMTs, transconductance reduction and decreasing the fT and fmax values up to 40% respect to the case using 60 W N2 plasma power. Although AFM (atomic force microscopy) results showed AlGaN and GaN surface roughness is not strongly affected by the N2-plasma, KFM (Kelvin force microscopy) surface analysis shows significant changes in the surface potential, trending to increase its values as the plasma power is higher. The whole results point at energetic ions inducing polarization-charge changes that affect dramatically to the 2-DEG charge density and the final characteristics of the HEMT devices. Therefore, we conclude that AlGaN surface is strongly sensitive to N2 plasma power conditions, which turn to be a key factor to achieve a good surface preparation prior to SiN passivation.

Manipulation, dissection, and lithography using modified tapping mode atomic force microscope

A modified tapping mode of the atomic force microscope (AFM) was introduced for manipulation, dissection, and lithography. By sufficiently decreasing the amplitude of AFM tip in the normal tapping mode and adjusting the setpoint, the tip-sample interaction can be efficiently controlled. This modified tapping mode has some characteristics of the AFM contact mode and can be used to manipulate nanoparticles, dissect biomolecules, and make lithographs on various surfaces. This method did not need any additional equipment and it can be applied to any AFM system.

Simulations of the Frequency Modulated Atomic Force Microscope (FM-AFM) nonlinear control system

The Frequency Modulated - Atomic Force Microscope (FM-AFM) is apowerful tool to perform surface investigation with true atomic resolution. The controlsystem of the FM-AFM must keep constant both the frequency and amplitude ofoscillation of the microcantilever during the scanning process of the sample. However,tip and sample interaction forces cause modulations in the microcantilever motion.A Phase-Locked Loop (PLL) is used as a demodulator and to generate feedback signalto the FM-AFM control system. The PLL performance is vital to the FM-AFMperformace since the image information is in the modulated microcantilever motion.Nevertheless, little attention is drawn to PLL performance in the FM-AFM literature.Here, the FM-AFM control system is simulated, comparing the performancefor di erent PLL designs.

Kaolinite platelet orientation for XRD and AFM applications

The structure-building phenomena within clay aggregates are governed by forces acting between clay particles. The nature of such forces is important to understand in order to manipulate the aggregate structure for applications such as settling and dewatering. A parallel particle orientation is required when conducting force measurements acting between the basal planes of clay mineral platelets using atomic force microscopy (AFM). In order to prepare a film of clay particles with the optimal orientation for conducting AFM measurements, the influences of particle concentration in suspension, suspension pH and particle size on the clay platelet orientation were investigated using scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods. From these investigations, we conclude that high clay (dry mass) concentrations and larger particle diameters (up to 5 µm) in suspension result in random orientation of platelets on the substrate. The best possible laminar orientation in the clay dried film as represented in the XRD by the 001/020 intensity ratio of more than 150 and by SE micrograph assessments, was obtained by drying thin layers from 0.2 wt% of -5 µm clay suspensions at pH 10.5. These dried films are stable and suitable for close-approach AFM studies in solution.

AFM study of morphological changes associated with electrochemical solid--solid transformation of three-dimensional crystals of TCNQ to metal derivatives (metal= Cu, Co, Ni; TCNQ= tetracyanoquinodimethane)

In situ atomic force microscopy (AFM) allows images from the upper face and sides of TCNQ crystals to be monitored during the course of the electrochemical solid–solid state conversion of 50 × 50 μm2 three-dimensional drop cast crystals of TCNQ to CuTCNQ or M[TCNQ]2(H2O)2 (M = Co, Ni). Ex situ images obtained by scanning electron microscopy (SEM) also allow the bottom face of the TCNQ crystals, in contact with the indium tin oxide or gold electrode surface and aqueous metal electrolyte solution, to be examined. Results show that by carefully controlling the reaction conditions, nearly mono-dispersed, rod-like phase I CuTCNQ or M[TCNQ]2(H2O)2 can be achieved on all faces. However, CuTCNQ has two different phases, and the transformation of rod-like phase 1 to rhombic-like phase 2 achieved under conditions of cyclic voltammetry was monitored in situ by AFM. The similarity of in situ AFM results with ex situ SEM studies accomplished previously implies that the morphology of the samples remains unchanged when the solvent environment is removed. In the process of crystal transformation, the triple phase solid∣electrode∣electrolyte junction is confirmed to be the initial nucleation site. Raman spectra and AFM images suggest that 100% interconversion is not always achieved, even after extended electrolysis of large 50 × 50 μm2 TCNQ crystals.