Development of Plasmonic Nanoplatforms for Diagnostics, Therapy, and Sensing

Recent advances in nanotechnology have led to the application of nanoparticles in a wide variety of fields. In the field of nanomedicine, there is great emphasis on combining diagnostic and therapeutic modalities into a single nanoparticle construct (theranostics). In particular, anisotropic nanoparticles have shown great potential for surface-enhanced Raman scattering (SERS) detection due to their unique optical properties. Gold nanostars are a type of anisotropic nanoparticle with one of the highest SERS enhancement factors in a non-aggregated state. By utilizing the distinct characteristics of gold nanostars, new plasmonic materials for diagnostics, therapy, and sensing can be synthesized. The work described herein is divided into two main themes. The first half presents a novel, theranostic nanoplatform that can be used for both SERS detection and photodynamic therapy (PDT). The second half involves the rational design of silver-coated gold nanostars for increasing SERS signal intensity and improving reproducibility and quantification in SERS measurements.

The theranostic nanoplatforms consist of Raman-labeled gold nanostars coated with a silica shell. Photosensitizer molecules for PDT can be loaded into the silica matrix, while retaining the SERS signal of the gold nanostar core. SERS detection and PDT are performed at different wavelengths, so there is no interference between the diagnostic and therapeutic modalities. Singlet oxygen generation (a measure of PDT effectiveness) was demonstrated from the drug-loaded nanocomposites. In vitro testing with breast cancer cells showed that the nanoplatform could be successfully used for PDT. When further conjugating the nanoplatform with a cell-penetrating peptide (CPP), efficacy of both SERS detection and PDT is enhanced.

The rational design of plasmonic nanoparticles for SERS sensing involved the synthesis of silver-coated gold nanostars. Investigation of the silver coating process revealed that preservation of the gold nanostar tips was necessary to achieve the increased SERS intensity. At the optimal amount of silver coating, the SERS intensity is increased by over an order of magnitude. It was determined that a majority of the increased SERS signal can be attributed to reducing the inner filter effect, as the silver coating process moves the extinction of the particles far away from the laser excitation line. To improve reproducibility and quantitative SERS detection, an internal standard was incorporated into the particles. By embedding a small-molecule dye between the gold and silver surfaces, SERS signal was obtained both from the internal dye and external analyte on the particle surface. By normalizing the external analyte signal to the internal reference signal, reproducibility and quantitative analysis are improved in a variety of experimental conditions.

Site controlled red-yellow-green light emitting InGaN quantum discs on nano-tipped GaN rods

We report a method of growing site controlled InGaN multiple quantum discs (QDs) at uniform wafer scale on coalescence free ultra-high density (>80%) nanorod templates by metal organic chemical vapour deposition (MOCVD). The dislocation and coalescence free nature of the GaN space filling nanorod arrays eliminates the well-known emission problems seen in InGaN based visible light sources that these types of crystallographic defects cause. Correlative scanning transmission electron microscopy (STEM), energy-dispersive X-ray (EDX) mapping and cathodoluminescence (CL) hyperspectral imaging illustrates the controlled site selection of the red, yellow and green (RYG) emission at these nano tips. This article reveals that the nanorod tips' broad emission in the RYG visible range is in fact achieved by manipulating the InGaN QD's confinement dimensions, rather than significantly increasing the In%. This article details the easily controlled method of manipulating the QDs dimensions producing high crystal quality InGaN without complicated growth conditions needed for strain relaxation and alloy compositional changes seen for bulk planar GaN templates.

Seasonal variations in surface metabolite composition of Fucus vesiculosus and Fucus serratus sampled at outer Kiel Fjord (August 2012 - July 2013)

The chemical composition of surface associated metabolites of two Fucus species (Fucus vesiculosus and Fucus serratus) was analysed by means of gas chromatography-mass spectrometry (GC-MS) to describe temporal patterns in chemical surface composition. Method: The two perennial brown macroalgae F. vesiculosus and F. serratus were sampled monthly at Bülk, outer Kiel Fjord, Germany (54°27'21 N / 10°11'57 E) over an entire year (August 2012 - July 2013). Per month and species six non-fertile Fucus individuals were collected from mixed stands at a depth of 0.5 m under mid water level. For surface extraction approx. 50 g of the upper 5-10 cm apical thalli tips were cut off per species. The surface extraction of Fucus was performed according to the protocol of de Nys and co-workers (1998) with minor modifications (see Rickert et al. 2015). GC/EI-MS measurements were performed with a Waters GCT premier (Waters, Manchester, UK) coupled to an Agilent 6890N GC equipped with a DB-5 ms 30 m column (0.25 mm internal diameter, 0.25 mM film thickness, Agilent, USA). The inlet temperature was maintained at 250°C and samples were injected in split 10 mode. He carrier gas flow was adjusted to 1 ml min-1. Alkanes were used for referencing of retention times. For further details (GC-MS sample preparation and analysis) see the related publication (Rickert et al. submitted to PLOS ONE).

Seawater carbonate chemistry and growth rate during experiments with coral Acropora cervicornis, 2005

The growth rate of Acropora cervicornis branch tips maintained in the laboratory was measured before, during, and after exposure to elevated nitrate (5 and 10 µM NO3-), phosphate (2 and 4 µM P-PO43) and/or pCO2 (CO2 ~700 to 800 µatm). The effect of increased pCO2 was greater than that of nutrient enrichment alone. High concentrations of nitrate or phosphate resulted in significant decreases in growth rate, in both the presence and absence of increased pCO2. The effect of nitrate and phosphate enrichment combined was additive or antagonistic relative to nutrient concentration and pCO2 level. Growth rate recovery was greater after exposure to increased nutrients or CO2 compared to increased nutrients and CO2. If these results accurately predict coral response in the natural environment, it is reasonable to speculate that the survival and reef-building potential of this species will be significantly negatively impacted by continued coastal nutrification and projected pCO2 increases.

Seawater carbonate chemistry, physiology and skeletal mineralogy of coralline alga Corallina elongata in a laboratory experiment

Marine organisms inhabiting environments where pCO2/pH varies naturally are suggested to be relatively resilient to future ocean acidification. To test this hypothesis, the effect of elevated pCO2 was investigated in the articulated coralline red alga Corallina elongata from an intertidal rock pool on the north coast of Brittany (France), where pCO2 naturally varied daily between 70 and 1000 µatm. Metabolism was measured on algae in the laboratory after they had been grown for 3 weeks at pCO2 concentrations of 380, 550, 750 and 1000 µatm. Net and gross primary production, respiration and calcification rates were assessed by measurements of oxygen and total alkalinity fluxes using incubation chambers in the light and dark. Calcite mol % Mg/Ca (mMg/Ca) was analysed in the tips, branches and basal parts of the fronds, as well as in new skeletal structures produced by the algae in the different pCO2 treatments. Respiration, gross primary production and calcification in light and dark were not significantly affected by increased pCO2. Algae grown under elevated pCO2 (550, 750 and 1000 µatm) formed fewer new structures and produced calcite with a lower mMg/Ca ratio relative to those grown under 380 µatm. This study supports the assumption that C. elongata from a tidal pool, where pCO2 fluctuates over diel and seasonal cycles, is relatively robust to elevated pCO2 compared to other recently investigated coralline algae.

Seawater carbonate chemistry and calcification during experiments with corals, 2003

Biogenic calcification is influenced by the concentration of available carbonate ions. The recent confirmation of this for hermatypic corals has raised concern over the future of coral reefs because [CO3] is a decreasing function of increasing pCO2 in the atmosphere. As one of the overriding features of coral reefs is their diversity, understanding the degree of variability between species in their ability to cope with a change in [CO3] is a priority. We cultured four phylogenetically and physiologically different species of hermatypic coral (Acropora verweyi, Galaxea fascicularis, Pavona cactus and Turbinaria reniformis) under 'normal' (280 µmol/kg) and 'low' (140 µmol/kg) carbonate-ion concentrations. The effect on skeletogenesis was investigated quantitatively (by calcification rate) and qualitatively (by microstructural appearance of growing crystalline fibres using scanning electron microscopy (SEM)). The 'low carbonate' treatment resulted in a significant suppression of calcification rate and a tendency for weaker crystallization at the distal tips of fibres. However, while the calcification rate was affected uniformly across species (13-18% reduction), the magnitude of the microstructural response was highly species specific: crystallization was most markedly affected in A. verweyi and least in T. reniformis. These results are discussed in relation to past records and future predictions of carbonate variability in the oceans.

Mandibular Torus : A Synthesis of New and Previously Reported Data and a Discusssion of its Cause

Using original data on 1,5000 mandibles, but mainly previously published data, I present a overview of the distribution characteristics of mandibular torus and a hypothesis concerning its cause. Pedigree studies have established that genetic factors influence torus development. Extrinsic factors are strongly implicated by other evidence: prevalence among Arctic peoples, effect of dietary change, age regression, preponderance in males and on the right side, effect of cranial deformation, concurrence with palatine torus and maxillary alveolar exostoses, and clinical evidence. I propose that the primary factor is masticatory stress. According to a mechanism suggested by orthodontic research, the horizontal component of bite force tips the lower canine, premolars and first molar so that their root apices exert pressure on the periodontal membrane, causing formation of new bone on the lingual cortical plate of the alveolar process. Thus formed, the hyperostosis is vulnerable to trauma and its periosteal covering becomes bruised causing additional deposition of bone. Genes influence torus indirectly through their effect on occlusion. A patern of increased expressivity with incidence suggests that a quasicontinuous model may provide a better fit to pedigree data than single locus models previously tested.

SERS of meso-droplets supported on superhydrophobic wires allows exquisitely sensitive detection of dipicolinic acid, an anthrax biomarker, considerably below the infective dose

Surface-enhanced Raman measurements of <1 μL analyte/colloid meso-droplets on superhydrophobic wires with hydrophilic tips allowed dipicolinic acid, a spore biomarker for Bacillus anthracis (anthrax), to be detected at 10(-6) mol dm(-3). This is equivalent to 18 spores, significantly below the infective dose of 10(4) spores and 2 orders of magnitude better than previous measurements.

Recension av Andkjær, Søren, Bentsen, Peter & Ejbye-Ernst, Niels (2009) ”Friluftsliv: Natur, samfund og pædagogik” : Ambitiöst om friluftsliv i Danmark – kanske alltför ambitiöst...

Friluftsliv uppvisar ett uppsving som för många säkert är oväntat men som nog till stor del är i samklang med den skandinaviska tidsandan. Visserligen är det ett i huvudsak urbant fenomen, de senaste årens fokus på fysisk aktivitet, konditionsträning och fitness, aktiviteter som dessutom ofta äger rum inomhus i speciella kommersiellt drivna träningshallar – där är luften inte fri! – men trenden tar sig också uttryck i löpning eller joggning i urbana parkområden eller i lagom tuktad natur i anslutning till städer. Man kan tänka att steget inte skulle vara långt till verkliga naturupplevelser, och, som sagt, det finns ett uppsving. Det nymornade intresset för autentiska naturupplevelser kan säkert också bottna i en civilisationskritisk trend i det tidiga tredje millenniet, vars beståndsdelar spretar på ett sätt som gör det omöjligt att närmare skärskåda företeelsen i detta sammanhang. Istället konstaterar vi att forskningen varit kvick att fånga upp friluftsintresset, vilket inte minst märks i recensionsfloran på den här webbplatsen, som denna gång utvidgas med en recension av Friluftsliv: Natur, samfund og pædagogik av Peter Bentsen, Søren Andkjær och Niels Ejbye-Ernst (Munksgaard Danmark). Erik Backman, som disputerat i ämnet, har läst och recenserar, och han bjuder redaktörerna på många tips till förbättringar inför nästa upplaga av boken.

Does Tipping Help to Attract and Retain Better Service Workers?

A survey of several hundred restaurant servers in the United States found that servers’ attitudes toward working for tips and average tip sizes were weakly related (at best) to their service-orientation, intended job-tenure, and occupational-tenure. These findings suggest that tipping does not substantially help to attract and retain more service-oriented workers. Restaurateurs can eliminate tipping at their restaurants without fear that doing so will reduce the quality of their wait-staff.

The Performance Characteristics of a Surface-Modified Cutting Tool

In the past, many papers have been presented which show that the coating of cutting tools often yields decreased wear rates and reduced coefficients of friction. Although different theories are proposed, covering areas such as hardness theory, diffusion barrier theory, thermal barrier theory, and reduced friction theory, most have not dealt with the question of how and why the coating of tool substrates with hard materials such as Titanium Nitride (TiN), Titanium Carbide (TiC) and Aluminium Oxide (Al203) transforms the performance and life of cutting tools. This project discusses the complex interrelationship that encompasses the thermal barrier function and the relatively low sliding friction coefficient of TiN on an undulating tool surface, and presents the result of an investigation into the cutting characteristics and performance of EDMed surface-modified carbide cutting tool inserts. The tool inserts were coated with TiN by the physical vapour deposition (PVD) method. PVD coating is also known as Ion-plating which is the general term of the coating method in which the film is created by attracting ionized metal vapour in this the metal was Titanium and ionized gas onto negatively biased substrate surface. Coating by PVD was chosen because it is done at a temperature of not more than 5000C whereas chemical Vapour Deposition CVD process is done at very high temperature of about 8500C and in two stages of heating up the substrates. The high temperatures involved in CVD affects the strength of the (tool) substrates. In this study, comparative cutting tests using TiN-coated control specimens with no EDM surface structures and TiN-coated EDMed tools with a crater-like surface topography were carried out on mild steel grade EN-3. Various cutting speeds were investigated, up to an increase of 40% of the tool manufacturer’s recommended speed. Fifteen minutes of cutting were carried out for each insert at the speeds investigated. Conventional tool inserts normally have a tool life of approximately 15 minutes of cutting. After every five cuts (passes) microscopic pictures of the tool wear profiles were taken, in order to monitor the progressive wear on the rake face and on the flank of the insert. The power load was monitored for each cut taken using an on-board meter on the CNC machine to establish the amount of power needed for each stage of operation. The spindle drive for the machine is an 11 KW/hr motor. Results obtained confirmed the advantages of cutting at all speeds investigated using EDMed coated inserts, in terms of reduced tool wear and low power loads. Moreover, the surface finish on the workpiece was consistently better for the EDMed inserts. The thesis discusses the relevance of the finite element method in the analysis of metal cutting processes, so that metal machinists can design, manufacture and deliver goods (tools) to the market quickly and on time without going through the hassle of trial and error approach for new products. Improvements in manufacturing technologies require better knowledge of modelling metal cutting processes. Technically the use of computational models has a great value in reducing or even eliminating the number of experiments traditionally used for tool design, process selection, machinability evaluation, and chip breakage investigations. In this work, much interest in theoretical and experimental investigations of metal machining were given special attention. Finite element analysis (FEA) was given priority in this study to predict tool wear and coating deformations during machining. Particular attention was devoted to the complicated mechanisms usually associated with metal cutting, such as interfacial friction; heat generated due to friction and severe strain in the cutting region, and high strain rates. It is therefore concluded that Roughened contact surface comprising of peaks and valleys coated with hard materials (TiN) provide wear-resisting properties as the coatings get entrapped in the valleys and help reduce friction at chip-tool interface. The contributions to knowledge: a. Relates to a wear-resisting surface structure for application in contact surfaces and structures in metal cutting and forming tools with ability to give wear-resisting surface profile. b. Provide technique for designing tool with roughened surface comprising of peaks and valleys covered in conformal coating with a material such as TiN, TiC etc which is wear-resisting structure with surface roughness profile compose of valleys which entrap residual coating material during wear thereby enabling the entrapped coating material to give improved wear resistance. c. Provide knowledge for increased tool life through wear resistance, hardness and chemical stability at high temperatures because of reduced friction at the tool-chip and work-tool interfaces due to tool coating, which leads to reduced heat generation at the cutting zones. d. Establishes that Undulating surface topographies on cutting tips tend to hold coating materials longer in the valleys, thus giving enhanced protection to the tool and the tool can cut faster by 40% and last 60% longer than conventional tools on the markets today.

Consumer Focus: Getting Static about Your Satellite or Cable TV Complaint?, November 2016

The Attorney General’s Consumer Protection Division receives hundreds of calls and consumer complaints every year. Follow these tips to avoid unexpected expense and disappointments. This record is about: New Credit and Debit Card Chips

Gewebeansatz-Strukturen auf pyritisierten Steinkernen von Ammonoideen

3400 pyritized internal moulds of Upper Devonian, Triassic, Jurassic and Lower Cretaceous ammonoids show various soft tissue attachment structures. They are preserved as regularly distributed black patterns on the moulds. All structures can be interpreted as attachment areas of muscles, ligaments and intracameral membranes. Paired structures are developed along the umbilicus and on the flanks of the moulds, unpaired ones appear on the middle of their dorsal and ventral sides. Strong lateral muscles cause paired twin lines on the flanks of the phragmocone and of the body chamber. A ventral muscle is deduced from small rounded or crescent shaped spots in front of each septum on the ventral side. These spots are often connected, forming a band-like structure. Broad dark external bands on the ventral side of the phragmocone, ventral preseptal areas in the posterior part of the living chamber, small twin lines or oval shaped areas on the ventral side of the living chamber represent paired or unpaired attachment areas of the hyponome muscle. A middorsal muscle is documented by small roughened areas in front of each dorsal lobe. Dark spots along the umbilicus, often connected and thus forming a band-like structure (tracking band), are remains of a pair of small dorsolateral muscles at the posterior end of the soft body. Dark bands, lines and rows of small crescent shaped structures behind the tips of sutural lobes are due to spotlike fixation places of the posterior part of the mantle and their translocation before subsequent septal secretion. Devonian goniatites had a paired system of lateral and ventrolateral muscles preserved on the moulds as black or incised lines on the flanks of the living chamber and as dark preseptal areas, ventrally indented. These structures represent the attachment areas of paired lateral cephalic and paired ventral hyponome retractors. Fine black lines on the phragmocone situated parallel to the sutures (pseudosutures) represent a rhythmical secretion of camera! membranes during softbody translocation. Goniatites had a paired system of lateral and ventrolateral muscles, whilst Neoammonoids have a paired lateral and dorsolateral system, and, additionally, an unpaired system on the ventral and on the dorsal side. Mesoammonoids show only a paired lateral and an unpaired dorsal one. Fine black lines situated parallel to the saddles and behind the lobes of the suture line can be interpreted as structures left during softbody translocation and a temporary attachment of rhythmical secreted cameral membranes. Cameral membranes had supported the efficiency of the phragmocone. Only some of the observed structures are also present in recent Nautilus. Differences in the form and position of attachment sites between ammonoids and recent Nautilus indicate different soft body organizations between ammonoids and nautiloids. The attachment structures of goniatites especially of tornoceratids can be compared with those of Nautilus which indicates Richter - Gewebeansatz-Strukturen bei Ammonoideen 3 a comparable mode of life. Differences in the form and position of attachment structures between goniatites and ammonites may indicate an increasing differentiation of the muscular system in the phylogeny of this group. Different soft body organization may depend on shell morphology and on a different mode of life. On the modification or reduction of distinct muscle systems ammonoids can be assigned to different ecotypes. Based on shell morphology and the attachment areas of cephalic and hyponome retractor muscles two groups can be subdivided: - Depressed, evolute morphotypes with longidome body-chambers show only small ventral hyponome retractor muscles. Lateral cephalic retractors are not developed. These morphotypes are adapted to a demersal mode of life. Without strong cephalic retractor muscles no efficient jet propulsion can be produced. These groups represent vertical migrants with efficient phragmocone properties (multilobate sutures, cameral membranes, narrow septal spacing). - Compressed, involute moiphotypes with brevidome body-chambers show strong cephalic and hyponome retractor muscles and represent a group of active swimmers. These morphotypes were able to live at different depths, in the free water column or/and near the seafloor. They are not confined only to one habitat. Most of the examined genera and species belong to this group. Changes of the attachment structures in the course of ontogeny confirm that juveniles of Amaltheus and Quenstedtoceras lived as passive planche drifters in upper and intermediate parts of the free water column after hatching. At the end of the juvenile stage with a shell diameter of 0,3 - 0,5 cm cephalic retractor muscles developed. With the beginning of an active swimming mode of life (neanic stage) the subadult animals left the free water column and moved into shallow water habitats. Fuciniceras showed no marked changes in the attachment structures during ontogeny. This indicates that there occur no differences in the mode of life between juvenile and adult growth stages. Based on attachment structures and shell morphology of Devonian goniatites their relation to the systematic position permits statements about probable phylogenetic relationships between the Cheiloceratidae and Tornoceratidae. In some cases attachment structures of ammonites permit statements about phylogenetic relationships on family and genus level.

Validation of the effects of a single one second hypochlorite floral dip on Botrytis cinerea incidence following long-term shipment of cut roses

The effect of a pre-shipment hypochlorite treatment on botrytis incidence was evaluated in a large number of rose cultivars and under different long-term storage conditions. Application parameters, stability and sources of hypochlorite were investigated. Irrespective of the type of packaging and shipment conditions, roses that received a pre-shipment treatment with 100 to 150 mg/L hypochlorite showed a significantly decreased botrytis incidence compared to non-hypochlorite treated roses. The hypochlorite treatment generally was more effective than a comparable treatment with commercial fungicides. Dipping the flower heads for approximately one second in a hypochlorite solution was more effective than spraying the heads. In few cases minor hypochlorite-induced damage on the petal tips was observed at higher concentrations (>200 mg/L). Apart from the effect on botrytis incidence, the treatment resulted in reduced water loss that may have an additional beneficial effect on the eventual flower quality. It is concluded that, apart from other obvious measures to reduce botrytis incidence (prevention of high humidity at the flower heads) a pre-shipment floral dip in 100 to 150 mg/L hypochlorite from commercial household bleach is an easy and cost effective way to reduce botrytis incidence following long term storage/transportation of roses. © 2015, International Society for Horticultural Science. All rights reserved.

'Artificial Immune Systems Tutorial'

The biological immune system is a robust, complex, adaptive system that defends the body from foreign pathogens. It is able to categorize all cells (or molecules) within the body as self-cells or non-self cells. It does this with the help of a distributed task force that has the intelligence to take action from a local and also a global perspective using its network of chemical messengers for communication. There are two major branches of the immune system. The innate immune system is an unchanging mechanism that detects and destroys certain invading organisms, whilst the adaptive immune system responds to previously unknown foreign cells and builds a response to them that can remain in the body over a long period of time. This remarkable information processing biological system has caught the attention of computer science in recent years. A novel computational intelligence technique, inspired by immunology, has emerged, called Artificial Immune Systems. Several concepts from the immune have been extracted and applied for solution to real world science and engineering problems. In this tutorial, we briefly describe the immune system metaphors that are relevant to existing Artificial Immune Systems methods. We will then show illustrative real-world problems suitable for Artificial Immune Systems and give a step-by-step algorithm walkthrough for one such problem. A comparison of the Artificial Immune Systems to other well-known algorithms, areas for future work, tips & tricks and a list of resources will round this tutorial off. It should be noted that as Artificial Immune Systems is still a young and evolving field, there is not yet a fixed algorithm template and hence actual implementations might differ somewhat from time to time and from those examples given here.