Design of switchable "smart" surfaces for biomedical and nanotechnological applications

Thesis (Ph. D.)--Harvard-MIT Division of Health Sciences and Technology, June 2005.Includes bibliographical references.Chapter 1. An Introduction to Self-Assembled Monolayers & Surface Characterization A brief summary of the formation, structure, and characterization techniques of self assembled monolayers (SAMs) is described. The characterization techniques include contact angle goniometry, ellipsometry, grazing-angle Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), sum-frequency generation spectroscopy (SFG), and atomic force microscopy (AFM). Chapter 2. A Reversibly Switching Surface The design of surfaces that exhibit dynamic changes in interfacial properties such as wettability in response to an electrical potential is described. The change in wetting behavior was caused by surface-confined, single-layered molecules undergoing conformational transitions between a hydrophilic and a moderately hydrophobic state. Reversible conformational transitions were confirmed both at a molecular level using sum-frequency generation spectroscopy and at a macroscopic level using contact angle measurements. This type of surface design enables amplification of conformational transitions at a molecular level to macroscopic changes in surface properties without altering the chemical identity of the surface. Such reversibly switching surfaces may open new opportunities in interfacial engineering.Chapter 3. A Synthetic Chemical Route for the Formation of Homogeneously- Mixed Self-Assembled Monolayers A novel way to produce self-assembled monolayers (SAMs) uniformly mixed on the molecular length scale is described.(cont.) Initially, a precursor SAM was formed from molecules that are derived from 16-mercaptohexadecanoic acid (MHA) and contain a globular end group. Self-assembly of these molecules resulted in a SAM that is densely packed with respect to the space-filling end groups, but shows low-density packing with respect to the hydrophobic chains. Subsequent cleavage of the space-filling end groups established a low-density SAM of MHA. A mixed monolayer of MHA and n-butanethiol was formed by backfilling the low-density monolayer of MHA with the corresponding alkanethiol. The new "mixed" SAM was characterized by optical ellipsometry, contact angle goniometry, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FT-IR), cyclic voltammetry (CV), and reductive desorption voltammetry. The results indicate a uniformly mixed monolayer as compared to a SAM generated by coadsorption of mixtures of the same MHA and n-butanethiol molecules. This approach provides a way to produce SAMs that are uniformly mixed using a synthetic chemical route, which affords considerable flexibility in composition and also in the ratio of the different molecules in the mixed SAM. Chapter 4.(cont.) Design of Oligonucleotide Arrays Using Homogeneously Mixed Self - Assembled Monolayers We have employed two quantitative techniques, quart-crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance imaging (SPR) to quantify the hybridization efficiency of a 25-mer oligonucleotide probe to two different surfaces: a dense 16-mercaptohexadecanoic acid self-assembled monolayer (MHA SAM) and a homogeneously-mixed (HM) SAM generated from the method described in Chapter 3 that allows for regular spacing of functional -COOH groups. This reduced density of functional groups led to reduced attachment of oligonucleotide probes to the surface, increasing the area per probe, and allowed more space in which complimentary sequence can bind. Reducing the density of immobilized probes led to the improvement in hybridization efficiency as demonstrated in both SPR and QCM-D results, which are comparable to previous reports. Our method paves the way for customizing binding efficiency and target probe density based on the distance between functional groups. By changing the headgroup size of the precursor monolayer, different distances between functional group can be formed, allowing for an ability to tailor distances between molecules. This method may allow for improvement in DNA array technology.Chapter 5. Long-Term Stability of Self-Assembled Monolayers in Biological Media The study of long term stability of self-assembled monolayer (SAM) in biological media is of importance in evaluating its usefulness for applications in implantable biochips, biosensors, or biological microelectromechanical system (bioMEMs) devices for drug delivery.(cont.) To minimize biofouling effects, researchers have investigated protein/cell adhesion resistant surface-bound materials such as poly(ethylene glycol) or oligo(ethylene glycol) terminated self-assembled monolayers. However, no long term study in biological media has been done. To address the issue of moderate to long-term stability of SAMs for bioMEMS device modification, alkanethiol and oligo(EG) terminated alkanethiol monolayers were prepared and studied after immersion in either phosphate buffer saline (PBS) or calf serum. Here, undecanethiol (CllH23SH) and tri(ethylene glycol) terminated undecanethiol (HO(C2H40)3C H22SH) self-assembled monolayers (SAMs) on clean gold surfaces were prepared and characterized. The SAMs were then immersed into either phosphate buffered saline (PBS) or calf serum. The SAM samples were emmersed and investigated using several analytical techniques at numerous points over the next 35 days. Contact angles and current densities in voltammetry changed dramatically for the PBS samples over the time period, particularly after 21 days. Results indicate substantial loss of the integrity of the SAM. Similar alterations with time were observed for the calf serum samples in both contact angle and voltammetry measurements. X-ray photoelectron spectroscopy indicates that the likely origin is desorption of the alkanethiol moiety as evidenced by appreciable loss of the S 2p signal after 35 days. Additionally, this work may serve as a starting point for further studies of surface chemical modification methods for moderate to long-term minimization of biofouling for in vivo applications.by Thanh-Nga T. Tran.Ph.D

Treatment efficiency and membrane fouling of a lab-scale anaerobic membrane bioreactor treating dilute municipal wastewater

The study aims to investigate the application of anaerobic processes coupled with membrane filtration for treating dilute municipal wastewater in Hanoi city

In-band pumped conical refraction Nd:KGW laser

We have demonstrated an in-band pumped conical refraction (CR) Nd: KGW laser. The CR laser was diode-pumped at 910 nm and produced an output power of 1.15 W at 1069 nm

Internally Controlled, Generic Real-Time PCR for Quantification and Multiplex Real-Time PCR with Serotype-Specific Probes for Serotyping of Dengue Virus Infections

Dengue has become a global public health problem and a sensitive diagnostic test for early phase detection can be life saving. An internally controlled, generic real-time PCR was developed and validated by testing serial dilutions of a DENV positive control RNA in the presence of a fixed amount of IC with results showing a good linearity (R2 = 0.9967) and a LOD of at least 1.95 × 104 copies/mL. Application of the generic PCR on 136 patient samples revealed a sensitivity of 95.8% and specificity of 100%. A newly developed multiplex real-time PCR with serotype-specific probes allowed the serotyping of DENV for 80 out of 92 (87%) generic real-time PCR positive patients. Combined these real-time PCRs offer a convenient diagnostic tool for the sensitive and specific quantification of DENV in clinical specimens with the possibility for serotyping

Encouraging Dialogue around Social Issues with Latinx Students Through Literature Discussion and Culturally Relevant Literature

This teacher research study examines literature discussions with fourth and fifth grade Latinx students about books that reflect Latinx experiences. For this study, the following questions are explored (1) What social issues do students discuss in literature groups? (2) How do literary response strategies influence student dialogue? And (3) How does my theoretical frame influence my decision making as a teacher? Theories that informed the construction of the literature discussions and the decision making occurring throughout the study are examined closely. The theories intertwine and bridge education and students’ experiences as a resource in learning more about the educational setting. In this study, the discussions of students and the literature response strategies are explored as the data is analyzed to examine the student discussions around issues of immigration, family separation, borders, and so much more. The findings in this study indicate that the experiences of Latinx students are integral to the educational setting and an education that invites who they are enhances their learning experiences. Latinx students are eager for learning opportunities that invite their voices and stories. It is through the construction and assessment of the educational setting that educators can promote culturally responsive, relevant, and sustaining teaching experiences that go beyond the classroom setting. Latinx students build relationships with each other and their teachers as they engage in discussions that allow them to share and learn with each other. This study is a reminder of the crucial role teachers play in creating such powerful spaces and the value that Latinx students bring into the classroom when invited to discuss, engage, and create powerful learning experiences

Identifying Priority Health Conditions, Environmental Data, and Infrastructure Needs: A Synopsis of the Pew Environmental Health Tracking Project

In this article we describe the methodologic approaches of the Pew Environmental Health Commission at the Johns Hopkins Bloomberg School of Public Health used to identify priority environmental health conditions and develop recommendations to establish a national environmental public health tracking network. We present the results of a survey of public health and environmental practitioners to uncover state and local health tracking needs and priorities. We describe the steps that combined the findings from the state and local health tracking survey and a review of the state of the science on environmental impacts on health to identify priority health end points. Through an examination of national health and health care databases, we then describe trends and public health effects of those diseases that may be linked to the environment. Based on this analysis, respiratory diseases and neurologic diseases are recommended as priorities for tracking. Specific end points recommended for tracking include asthma and chronic respiratory diseases, and chronic neurodegenerative diseases such as multiple sclerosis. Based on trends in reported prevalence, consideration should also be given to developmental disabilities, reproductive disorders, and endocrine/metabolic disorders. Strengthening of current efforts to track cancer and birth defects should also be included as components of a nationwide health tracking network. Finally, we present the recommendations for environmental public health tracking. These recommendations provided the groundwork for the development of the Centers for Disease Control and Prevention’s National Environmental Public Health Tracking Progam that now includes 21 states, three cities, and three academic centers throughout the nation

Sugarcane mosaic virus infects Stenotaphrum secundatum in Australia

This study presents the first report of sugarcane mosaic virus (SCMV) infecting Stenotaphrum secundatum (buffalo grass) in Australia, from a turf farm in the Hunter Valley, New South Wales. The plant displayed mosaic symptoms and contained flexuous, filamentous virions of 700–750 × 10–11 nm typical of members of the genus Potyvirus. Infection of the sample by SCMV was confirmed by double antibody sandwich ELISA and RT-PCR amplification of the coat protein coding region of the viral genome. In a phylogenetic analysis, the buffalo grass isolate was sister to a clade of maize-infecting isolates of SCMV from eastern Africa and was 75.8% and 79.4% identical to the exemplar isolate of SCMV at nucleotide and amino acid levels, respectively

Bermuda grass latent virus in Australia: genome sequence, sequence variation, and new hosts

Bermuda grass latent virus (BGLV; genus Panicovirus) is identified for the first time in Australia and in only the second country after the USA. A full-length genome sequence was obtained, which has 97% nucleotide sequence identity to that of the species exemplar isolate. Surveys for BGLV, utilising a newly designed universal panicovirus RT-PCR assay for diagnosis, demonstrated widespread infection by this virus in a broad variety of Bermuda grass cultivars (Cynodon dactylon and C. dactylon × C. transvaalensis) grown in both New South Wales and Queensland. The virus was also detected in Rhodes grass (Chloris gayana) and Kikuyu grass (Cenchrus clandestinus), which are both important pasture grasses in subtropical Australia, and the latter is also grown as turf. Furthermore, the Rhodes grass plant, which had strong mosaic symptoms, was also infected with sugarcane mosaic virus, warranting further investigations as to whether synergistic interactions occur between these two viruses