Investigation of the ligand shells of homo-ligand and mixed-ligand monolayer protected metal nanoparticles : a scanning tunneling microscopy study

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2007.Includes bibliographical references.Monolayer Protected Metal Nanoparticles have recently found widespread use in and are the focus of intensive study in many areas of scientific research ranging from biology to physics to medicine. Consisting of a nanoscale, crystalline, metallic core surrounded by a self-assembled monolayer of ligands (a 3-D SAM or ligand shell), their appeal and utility stem from their numerous unique properties-many of which arise and are modulated by the intimate spatial and electronic contact between core and shell. The ligand shell controls the particle's interactions with its environment (e.g. sensing, assembly, and electron transfer ability). Furthermore, the ability to manipulate and assemble such nanomaterials through the ligand shell is paramount to their incorporation into and the development of new nanoparticle based materials and devices. However, little is known of the exact composition and packing arrangements of molecules within the ligand shell, and even less so on how to control the resulting nanostructuring. In this thesis we present a Scanning Tunneling Microscopy investigation of the ligand shells of homo- and mixed-ligand metal nanoparticles.(cont.) We develop an understanding and model of the ligand arrangements around the nanoparticle core, showing that the multifaceted, high curvature, and topologically spherical nature of the core results in a 3-D SAM that has many differences from its 2-D SAM counterparts. We show that the core curvature (and correspondingly, the changing facet to edge ratio on the core surface) of the particles is the dominant driver for the packing and behavior of the ligand shell. Most interestingly, we find that when certain two-component, mixed SAMs are assembled around the particle core, the ligands phase-separate into ordered, ribbon-like domains, only a few molecules in width-a behavior never before seen on flat surfaces. We show that both the domain morphology and width can be controlled through the ligand shell composition and the particle core size, and that the observed phase-separation is a general phenomenon across nanoparticle compositions. We present these studies as a first step towards developing a complete model of and control over the ligand shell structure of nanoparticles.by Alicia M. Jackson.Ph.D

Effects of Oxygen Concentration and Culture Time on Porcine Nucleus Pulposus Cell Metabolism: An in vitro Study

Low back pain is a common ailment that affects millions of individuals each year and is linked to degeneration of the intervertebral discs in the spine. Intervertebral disc degeneration is known to result from an imbalance in anabolic and catabolic activity by disc cells. Due to the avascular nature of the intervertebral disc, oxygen deficiency may occur in the central nucleus pulposus (NP). The resulting hypoxia affects matrix regulation and energy metabolism of disc cells, although the mechanisms are not fully understood. This study investigates in vitro glucose consumption and gene expression by NP cells over time under varying oxygen tensions. Notochordal porcine NP cells were cultured in agarose discs at 21, 5, or 1% oxygen tension for 1, 5, or 10 days. The expression of 10 key matrix genes, as well as Brachyury (T), by NP cells was analyzed using RT-PCR. Glucose consumption was measured using a two-point method. Results show that culture time and oxygen tension significantly affect glucose consumption rates by porcine NP cells. There were also significant changes in T expression based on oxygen level and culture time. The 1% oxygen tension had a significantly higher T expression on day 10 than the other two groups, which may indicate a better maintenance of the notochordal phenotype. MMP 1 and 13 expression increased over time for all groups, while only the 5% group showed an increase over time for MMP 3. TIMP expression followed the direction of MMPs but to a lesser magnitude. Five percent and twenty-one percent oxygen tensions led to decreases in anabolic gene expression while 1% led to increases. Oxygen concentration and culture time significantly impacted glucose consumption rate and the gene expression of matrix regulatory genes with hypoxic conditions most accurately maintaining the proper NP phenotype. This information is valuable not only for understanding disc pathophysiology, but also for harnessing the potential of notochordal NP cells in therapeutic applications

Tensile energy dissipation and mechanical properties of the knee meniscus: relationship with fiber orientation, tissue layer, and water content

Introduction: The knee meniscus distributes and dampens mechanical loads. It is composed of water (∼70%) and a porous fibrous matrix (∼30%) with a central core that is reinforced by circumferential collagen fibers enclosed by mesh-like superficial tibial and femoral layers. Daily loading activities produce mechanical tensile loads which are transferred through and dissipated by the meniscus. Therefore, the objective of this study was to measure how tensile mechanical properties and extent of energy dissipation vary by tension direction, meniscal layer, and water content.Methods: The central regions of porcine meniscal pairs (n = 8) were cut into tensile samples (4.7 mm length, 2.1 mm width, and 0.356 mm thickness) from core, femoral and tibial components. Core samples were prepared parallel (circumferential) and perpendicular (radial) to the fibers. Tensile testing consisted of frequency sweeps (0.01–1Hz) followed by quasi-static loading to failure. Dynamic testing yielded energy dissipation (ED), complex modulus (E*), and phase shift (δ) while quasi-static tests yielded Young’s Modulus (E), ultimate tensile strength (UTS), and strain at UTS (εUTS). To investigate how ED is influenced by the specific mechanical parameters, linear regressions were performed. Correlations between sample water content (φw) and mechanical properties were investigated. A total of 64 samples were evaluated.Results: Dynamic tests showed that increasing loading frequency significantly reduced ED (p < 0.05). Circumferential samples had higher ED, E*, E, and UTS than radial ones (p < 0.001). Stiffness was highly correlated with ED (R2 > 0.75, p < 0.01). No differences were found between superficial and circumferential core layers. ED, E*, E, and UTS trended negatively with φw (p < 0.05).Discussion: Energy dissipation, stiffness, and strength are highly dependent on loading direction. A significant amount of energy dissipation may be associated with time-dependent reorganization of matrix fibers. This is the first study to analyze the tensile dynamic properties and energy dissipation of the meniscus surface layers. Results provide new insights on the mechanics and function of meniscal tissue

Long‐term trends in the distribution, abundance and impact of native “injurious” weeds

Questions: How can we quantify changes in the distribution and abundance of injurious weed species (Senecio jacobaea, Cirsium vulgare, Cirsium arvense, Rumex obtusifolius, Rumex crispus and Urtica dioica), over long time periods at wide geographical scales? What impact do these species have on plant communities? To what extent are changes driven by anthropogenically induced drivers such as disturbance, eutrophication and management? Location: Great Britain. Methods: Data from national surveys were used to assess changes in the frequency and abundance of selected weed species between 1978 and 2007. This involved novel method development to create indices of change, and to relate changes in distribution and abundance of these species to plant community diversity and inferred changes in resource availability, disturbance and management. Results: Three of the six weed species became more widespread in GB over this period and all of them increased in abundance (in grasslands, arable habitats, roadsides and streamsides). Patterns were complex and varied by landscape context and habitat type. For most of the species, there were negative relationships between abundance, total plant species richness, grassland, wetland and woodland indicators. Each individual species responds to a different combination of anthropogenic drivers but disturbance, fertility and livestock management significantly influenced most species. Conclusions: The increase in frequency and abundance of weeds over decades has implications for landscape‐scale plant diversity, fodder yield and livestock health. This includes reductions in plant species richness, loss of valuable habitat specialists and homogenisation of vegetation communities. Increasing land‐use intensity, excessive nutrient input, overgrazing, sward damage, poaching and bare ground in fields and undermanagement or too frequent cutting on linear features may have led to increases in weeds. These weeds do have conservation value so we are not advocating eradication, rather co‐existence, without dominance. Land management policy needs to adapt to benefit biodiversity and agricultural productivity

Sturgeon in the Sacramento–San Joaquin Watershed: New Insights to Support Conservation and Management

The goal of a day-long symposium on March 3, 2015, Sturgeon in the Sacramento–San Joaquin Watershed: New Insights to Support Conservation and Management, was to present new information about the physiology, behavior, and ecology of the green (Acipenser medirostris) and white sturgeon (Acipenser transmontanus) to help guide enhanced management and conservation efforts within the Sacramento–San Joaquin watershed. This symposium identified current unknowns and highlighted new electronic tracking technologies and physiological techniques to address these knowledge gaps. A number of presentations, each reviewing ongoing research on the two species, was followed by a round-table discussion, in which each of the participants was asked to share recommendations for future research on sturgeon in the watershed. This article presents an in-depth review of the scientific information presented at the symposium with a summary of recommendations for future research

Interactive Effects of Racial Identity and Repetitive Head Impacts on Cognitive Function, Structural MRI-Derived Volumetric Measures, and Cerebrospinal Fluid Tau and A beta

Background: Factors of increased prevalence among individuals with Black racial identity (e.g., cardiovascular disease, CVD) may influence the association between exposure to repetitive head impacts (RHI) from American football and later-life neurological outcomes. Here, we tested the interaction between racial identity and RHI on neurobehavioral outcomes, brain volumetric measures, and cerebrospinal fluid (CSF) total tau (t-tau), phosphorylated tau (p-tau181), and Aβ1–42 in symptomatic former National Football League (NFL) players. Methods: 68 symptomatic male former NFL players (ages 40–69; n = 27 Black, n = 41 White) underwent neuropsychological testing, structural MRI, and lumbar puncture. FreeSurfer derived estimated intracranial volume (eICV), gray matter volume (GMV), white matter volume (WMV), subcortical GMV, hippocampal volume, and white matter (WM) hypointensities. Multivariate generalized linear models examined the main effects of racial identity and its interaction with a cumulative head impact index (CHII) on all outcomes. Age, years of education, Wide Range Achievement Test, Fourth Edition (WRAT-4) scores, CVD risk factors, and APOEε4 were included as covariates; eICV was included for MRI models. P-values were false discovery rate adjusted. Results: Compared to White former NFL players, Black participants were 4 years younger (p = 0.04), had lower WRAT-4 scores (mean difference = 8.03, p = 0.002), and a higher BMI (mean difference = 3.09, p = 0.01) and systolic blood pressure (mean difference = 8.15, p = 0.03). With regards to group differences on the basis of racial identity, compared to White former NFL players, Black participants had lower GMV (mean adjusted difference = 45649.00, p = 0.001), lower right hippocampal volume (mean adjusted difference = 271.96, p = 0.02), and higher p-tau181/t-tau ratio (mean adjusted difference = −0.25, p = 0.01). There was not a statistically significant association between the CHII with GMV, right hippocampal volume, or p-tau181/t-tau ratio. However, there was a statistically significant Race x CHII interaction for GMV (b = 2206.29, p = 0.001), right hippocampal volume (b = 12.07, p = 0.04), and p-tau181/t-tau ratio concentrations (b = −0.01, p = 0.004). Conclusion: Continued research on racial neurological disparities could provide insight into risk factors for long-term neurological disorders associated with American football play

Planet Hunters NGTS: New Planet Candidates from a Citizen Science Search of the Next Generation Transit Survey Public Data

We present the results from the first two years of the Planet Hunters Next Generation Transit Survey (NGTS) citizen science project, which searches for transiting planet candidates in data from the NGTS by enlisting the help of members of the general public. Over 8000 registered volunteers reviewed 138,198 light curves from the NGTS Public Data Releases 1 and 2. We utilize a user weighting scheme to combine the classifications of multiple users to identify the most promising planet candidates not initially discovered by the NGTS team. We highlight the five most interesting planet candidates detected through this search, which are all candidate short-period giant planets. This includes the TIC-165227846 system that, if confirmed, would be the lowest-mass star to host a close-in giant planet. We assess the detection efficiency of the project by determining the number of confirmed planets from the NASA Exoplanet Archive and TESS Objects of Interest (TOIs) successfully recovered by this search and find that 74% of confirmed planets and 63% of TOIs detected by NGTS are recovered by the Planet Hunters NGTS project. The identification of new planet candidates shows that the citizen science approach can provide a complementary method to the detection of exoplanets with ground-based surveys such as NGTS

Human Rabies and Rabies in Vampire and Nonvampire Bat Species, Southeastern Peru, 2007

After a human rabies outbreak in southeastern Peru, we collected bats to estimate the prevalence of rabies in various species. Among 165 bats from 6 genera and 10 species, 10.3% were antibody positive; antibody prevalence was similar in vampire and nonvampire bats. Thus, nonvampire bats may also be a source for human rabies in Peru