Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Bearbeitung von Fangproben mit neuen elektronischen Messmethoden

For 10 years the Institute for Fishing Technology, Hamburg (IFH) has been carrying out experiments in the brown shrimp fishery with beam trawls aiming at a reduction of unwanted bycatches. When the tests were transferred to commercial fishery conditions the personnel effort and costs increased markedly. It became e.g. necessary to install a deep-freeze chain to make it possible to evaluate more samples in the laboratory. This again required to increase the number of technicians for measuring the fish and shrimp samples, but also made it necessary to perform this work in the most rational and time-saving way by applying modern electronic aids. Though all samples still have to be sorted by species and have to be weighed and measured the introduction of electronic aids, however, like electronic measuring board and computer-aided image processing system, all weight and length data are immediately and digitally recorded after processing. They are transferred via a network to a server PC which stores them into a purpose-designed database. This article describes the applicationof two electronic systems: the measuring board (FM 100, Fa. SCANTROL), iniated by a project in the Norwegian Institute for Fishing Technology, and a computer-aided image processing system, focussing on measuring shrimps in their naturally flexed shape, also developed in the Institute for Fishing Technology in close collaboration with the University of Duisburg. These electronic recording systems allow the consistent and reproducible record of data independent of the changing day-to-day personal form of the staff operating them. With the help of these systems the number of measurements the laboratory could be maximized to 250 000 per year. This made it possible to evaluate, in 1999, 525 catch samples from 75 commercial hauls taken during 15 days at sea. The time gain in measuring the samples is about one third of the time previously needed (i.e. one hour per sample). An additional advantage is the immediate availability of the digitally stored data which enables rapid analyses of all finished subexperiments. Both systems are applied today in several institutes of the Federal Research Centre. The image processing system is now the standard measuring method in an international research project.

Historie und aktueller Stand des Internationalen Heringslarvensurveys in der Nordsee

Since years the International Herring Larvae Survey Program (IHLS) is an important and internationally established survey program in the North Sea. The IHLS serves the calibration of stock abundance estimates based on information from the commercial fishery and the method of Integrated Catch Analysis (ICA) which is a specific derivate of the Virtual Population Analysis (VPA). Meanwhile the IHLS database has been transferred from Aberdeen to Kiel and it has been agreed that the Institut für Meereskunde Kiel should continue to maintain this database and provide the abundance indices to be utilized by the ICES Herring Assessment Working Group as one of the means for assessing the state of the herring stock in the North Sea. For establishing the calculation procedure at Kiel, it was necessary to optimize both, the survey design and the index calculation. This article gives an overview over the survey’s history, it’s geography, the sampling design, the information content of the IHLS data base and the various methods of calculating the different indices necessary for the calibration.

Aspects of ecology of Owena reservoirs: implication on fish production

The article gives physical description of Owana reservoir, Nigeria. The reservoir was chemically and thermally stratified partial mixing of the water was observed during the rains. The concentration of major ions in the water showed distinct peculiarities. The captions (Na super(+), K super(+)Ca super(H),Ca super(Z), Mg super(++)) SO sub(4) super(2-) were relatively low. The water had high dissolved oxygen, it was acidic and also had low values of alkalinity, conductivity and total dissolved solids. About 61 plankton taxa belonging to 21 species were identified. The reservoir supports a commercial fishery of about fifteen fishermen with about fifteen species of fish caught daily with the aid of traps set and cast nets. Effective management of the lake will enhance fish production

2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Modelling Study On The Plasma Flow and Heat Transfer In A Laminar Arc Plasma Torch Operating At Atmospheric and Reduced Pressure

A modelling study is performed to investigate the characteristics of both plasma flow and heat transfer of a laminar non-transferred arc argon plasma torch operated at atmospheric and reduced pressure. It is found that the calculated flow fields and temperature distributions are quite similar for both cases at a chamber pressure of 1.0 atm and 0.1 atm. A fully developed flow regime could be achieved in the arc constrictor-tube between the cathode and the anode of the plasma torch at 1.0 atm for all the flow rates covered in this study. However the flow field could not reach the fully developed regime at 0.1 atm with a higher flow rate. The arc-root is always attached to the torch anode surface near the upstream end of the anode, i.e. the abruptly expanded part of the torch channel, which is in consistence with experimental observation. The surrounding gas would be entrained from the torch exit into the torch interior due to a comparatively large inner diameter of the anode channel compared to that of the arc constrictor-tube.

减压直流非转移弧等离子体射流速度的静电探针测量

组建了一套利用静电探针诊断技术测量减压直流非转移弧等离子体射流速度的实验系统.对以纯氩为工质的等离子体,在气流量1.25×10~(-4) kg/s、弧电流80A、真空室压力165 Pa的条件下,测量了射流的速度及其分布.结果表明射流在发生器出口处中心最高速度约为1 200 m/s,在半径20 mm处减小到635 m/s.沿射流轴线方向的速度梯度约为10 (ms~(-1))/mm.射流速度随着弧电流增加而缓慢单调增加;当真空室压力从165 Pa提高到2 kPa时,发生器出口轴线上的射流速度从1200 m/s降至570 m/s.

Terahertz time domain spectroscopy of amino acids and sugars

A time-domain spectrometer for use in the terahertz (THz) spectral range was designed and constructed. Due to there being few existing methods of generating and detecting THz radiation, the spectrometer is expected to have vast applications to solid, liquid, and gas phase samples. In particular, knowledge of complex organic chemistry and chemical abundances in the interstellar medium (ISM) can be obtained when compared to astronomical data. The THz spectral region is of particular interest due to reduced line density when compared to the millimeter wave spectrum, the existence of high resolution observatories, and potentially strong transitions resulting from the lowest-lying vibrational modes of large molecules.

The heart of the THz time-domain spectrometer (THz-TDS) is the ultrafast laser. Due to the femtosecond duration of ultrafast laser pulses and an energy-time uncertainty relationship, the pulses typically have a several-THz bandwidth. By various means of optical rectification, the optical pulse carrier envelope shape, i.e. intensity-time profile, can be transferred to the phase of the resulting THz pulse. As a consequence, optical pump-THz probe spectroscopy is readily achieved, as was demonstrated in studies of dye-sensitized TiO₂, as discussed in chapter 4. Detection of the terahertz radiation is commonly based on electro-optic sampling and provides full phase information. This allows for accurate determination of both the real and imaginary index of refraction, the so-called optical constants, without additional analysis. A suite of amino acids and sugars, all of which have been found in meteorites, were studied in crystalline form embedded in a polyethylene matrix. As the temperature was varied between 10 and 310 K, various strong vibrational modes were found to shift in spectral intensity and frequency. Such modes can be attributed to intramolecular, intermolecular, or phonon modes, or to some combination of the three.

Synthesis, structure, and photophysics of polypyridophenazine transition-metal complexes

The condensation of phenanthroline-5,6-dione (phendione) with polyamines is a versatile synthetic route to a wide variety of chelating ligands. Condensation with 2,3- napthalene diamine gives benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (bdppz) a ligand containing weakly-coupled orbitals of benzophenazine (bpz) and 2,2' -bipyridinde(bpy) character. The bpy character gives Re and Ru complexes excited-state redox properties; intramolecular electron transfer (ET) takes place to the bpz portion of the ligand. The charge-separated state so produced has an extraordinarily-long 50 µs lifetime. The slow rate of charge recombination arises from a combination of extremely weak coupling between the metal center and the bpz acceptor orbital and Marcus "inverted region" behavior. Molecular orbital calculations show that only 3% the electron density in the lowest unoccupied molecular orbital lies on the bpy atoms of bdppz, effectively trapping the transferred electron on the bpz portion. The rate of charge recombination decreases with increasing driving force, showing that these rates lie in the inverted region. Comparison of forward and back ET rates shows that donor-acceptor coupling is four orders of magnitude greater for photoinduced electron transfer than it is for thermal charge recombination.

Condensation of phendione with itself or tetramines gives a series of binucleating tetrapyridophenazine ligands of incrementally-varying coordination-site separation. When a photoredox-active metal center is attached, excited-state energy and electron transfer to an acceptor metal center at the other coordination site can be studied as a function of distance. A variety of monometallic and homo- and heterodimetallic tetrapyridophenazine complexes has been synthesized. Electro- and magnetochemistry show that no ground-state interaction exists between the metals in bimetallic complexes. Excited-state energy and electron transfer, however, takes place at rates which are invariant with increasing donor-acceptor separation, indicating that a very efficient coupling mechanism is at work. Theory and experiment have suggested that such behavior might exist in extended π-systems like those presented by these ligands.

Condensation of three equivalents of 4,5-dimethyl-1,2-phenylenediamine with hexaketocyclohexane gives the trinucleating ligand hexaazahexamethyltrinapthalene (hhtn). Attaching two photredox-active metal centers and a third catalytic center to hhtn provides means by which multielectron photocatalyzed reactions might be carried out. The coordination properties of hhtn have been examined; X-ray crystallographic structure determination shows that the ligand's constricted coordination pocket leads to distorted geometries in its mono- and dimetallic derivatives.

Predicting the effects of climate change on sea turtle nesting habitat in Florida

Rising global temperatures threaten the survival of many plant and animal species. Having already risen at an unprecedented rate in the past century, temperatures are predicted to rise between 0.3 and 7.5C in North America over the next 100 years (Hawkes et al. 2007). Studies have documented the effects of climate warming on phenology (timing of seasonal activities), with observations of early arrival at breeding grounds, earlier ends to the reproductive season, and delayed autumnal migrations (Pike et al. 2006). In addition, for species not suited to the physiological demands of cold winter temperatures, increasing temperatures could shift tolerable habitats to higher latitudes (Hawkes et al. 2007). More directly, climate warming will impact thermally sensitive species like sea turtles, who exhibit temperature-dependent sexual determination. Temperatures in the middle third of the incubation period determine the sex of sea turtle offspring, with higher temperatures resulting in a greater abundance of female offspring. Consequently, increasing temperatures from climate warming would drastically change the offspring sex ratio (Hawkes et al. 2007). Of the seven extant species of sea turtles, three (leatherback, Kemp’s ridley, and hawksbill) are critically endangered, two (olive ridley and green) are endangered, and one (loggerhead) is threatened. Considering the predicted scenarios of climate warming and the already tenuous status of sea turtle populations, it is essential that efforts are made to understand how increasing temperatures may affect sea turtle populations and how these species might adapt in the face of such changes. In this analysis, I seek to identify the impact of changing climate conditions over the next 50 years on the availability of sea turtle nesting habitat in Florida given predicted changes in temperature and precipitation. I predict that future conditions in Florida will be less suitable for sea turtle nesting during the historic nesting season. This may imply that sea turtles will nest at a different time of year, in more northern latitudes, to a lesser extent, or possibly not at all. It seems likely that changes in temperature and precipitation patterns will alter the distribution of sea turtle nesting locations worldwide, provided that beaches where the conditions are suitable for nesting still exist. Hijmans and Graham (2006) evaluate a range of climate envelope models in terms of their ability to predict species distributions under climate change scenarios. Their results suggested that the choice of species distribution model is dependent on the specifics of each individual study. Fuller et al. (2008) used a maximum entropy approach to model the potential distribution of 11 species in the Arctic Coastal Plain of Alaska under a series of projected climate scenarios. Recently, Pike (in press) developed Maxent models to investigate the impacts of climate change on green sea turtle nest distribution and timing. In each of these studies, a set of environmental predictor variables (including climate variables), for which ‘current’ conditions are available and ‘future’ conditions have been projected, is used in conjunction with species occurrence data to map potential species distribution under the projected conditions. In this study, I will take a similar approach in mapping the potential sea turtle nesting habitat in Florida by developing a Maxent model based on environmental and climate data and projecting the model for future climate data. (PDF contains 5 pages)

Thin metastructures with engineered thermal expansion

The geometry and constituent materials of metastructures can be used to engineer the thermal expansion coefficient. In this thesis, we design, fabricate, and test thin thermally stable metastructures consisting of bi-metallic unit cells and show how the coefficient of thermal expansion (CTE) of these metastructures can be finely and coarsely tuned by varying the CTE of the constituent materials and the unit cell geometry. Planar and three-dimensional finite element method modeling is used to drive the design and inform experiments, and predict the response of these metastructures. We demonstrate computationally the significance of out-of-plane effects in the metastructure response. We develop an experimental setup using digital image correlation and an infrared camera to experimentally measure full displacement and temperature fields during testing and accurately measure the metastructures’ CTE. We experimentally demonstrate high aspect ratio metastructures of Ti/Al and Kovar/Al which exhibit near-zero and negative CTE, respectively. We demonstrate robust fabrication procedures for thermally stable samples with high aspect ratios in thin foil and thin film scales. We investigate the lattice structure and mechanical properties of thin films comprising a near-zero CTE metastructure. The mechanics developed in this work can be used to engineer metastructures of arbitrary CTE and can be extended to three dimensions.

Reactions of small molecules facilitated by metal-acceptor interactions

The role of metal-acceptor interactions arising from M–BR3 and M–PR3 bonding is discussed with respect to reactions between first-row transition metals and N2, H2, and CO. Thermally robust, S = 1/2 (TPB)Co(H2) and (TPB)Co(N2) complexes (TPB = tris(2- (diisopropylphosphino)phenyl)borane) are described and the energetics of N2 and H2 binding are measured. The H2 and N2 ligands are bound more weakly in the (TPB)Co complexes than in related (SiP3)M(L) complexes (SiP3 = tris(2- (diisopropylphosphino)phenyl)silyl). Comparisons within and between these two ligand platforms allow for the factors that affect N2 (and H2) binding and activation to be delineated. The characterization and reactivity of (DPB)Fe complexes (DPB = bis(2- (diisopropylphosphino)phenyl)phenylborane) in the context of N2 functionalization and E–H bond addition (E = H, C, N, Si) are described. This platform allows for the one-pot transformation of free N2 to an Fe hydrazido(-) complex via an Fe aminoimide intermediate. The principles learned from the N2 chemistry using (DPB)Fe are applied to CO reduction on the same system. The preparation of (DPB)Fe(CO)2 is described as well as its reductive functionalization to generate an unprecedented Fe dicarbyne. The bonding in this highly covalent complex is discussed in detail. Initial studies of the reactivity of the Fe dicarbyne reveal that a CO-derived olefin is released upon hydrogenation. Alternative approaches to uncovering unusual reactivity using metal- acceptor interactions are described in Chapters 5 and 6, including initial studies on a new π-accepting tridentate diphosphinosulfinyl ligand and strategies for designing ligands that undergo site-selective metallation to generate heterobimetallic complexes.

Characterizing a resonator bolometer array

High-background applications such as climate monitoring, biology and security applications demand a large dynamic range. Under such conditions ultra-high sensitivity is not required. The resonator bolometer is a novel detector which is well-suited for these conditions. This device takes advantage of the high-density frequency multiplexing capabilities of superconducting microresonators while allowing for the use of high-Tc superconductors in fabrication, which enables a modest (1-4 K) operating temperature and larger dynamic range than is possible with conventional microresonators. The moderate operating temperature and intrinsic multiplexability of this device reduce cost and allow for large pixel counts, making the resonator bolometer especially suitable for the aforementioned applications. A single pixel consists of a superconducting microresonator whose light-absorbing area is placed on a thermally isolated island. Here we present experimental results and theoretical calculations for a prototype resonator bolometer array. Intrinsic device noise and noise equivalent power (NEP) under both dark and illuminated conditions are presented. Under dark conditions the device sensitivity is limited by the thermal noise fluctuations from the bolometer legs. Under the experimental illuminated conditions the device was photon noise limited.

Active phase control and frequency chirp effects on supercontinuum generation in high birefringence photonic crystal fiber

An acoustic-optics programmable dispersive filter (AOPDF) was first employed to actively control the linearly polarized femtosecond pump pulse frequency chirp for supercontinuum (SC) generation in a high birefringence photonic crystal fiber (PCF). By accurately controlling the second order phase distortion and polarization direction of incident pulses, the output SC spectrum can be tuned to various spectral energy distributions and bandwidths. The pump pulse energy and bandwidth are preserved in our experiment. It is found that SC with broader bandwidth can be generated with positive chirped pump pulses except when the chirp value is larger than the optimal value, and the same optimal value exists for the pump pulses polarized along the two principal axes. With optimal positive chirp, more than 78% of the pump energy can be transferred to below 750 nm. Otherwise, negative chirp will weaken the blue-shift broadening and the SC bandwidth. (C) 2007 Elsevier B.V. All rights reserved.

Short-pulse laser absorption via J x B heating in ultrahigh intensity laser plasma interaction

An analytical fluid model for JxB heating during the normal incidence by a short ultraintense linearly polarized laser on a solid-density plasma is proposed. The steepening of an originally smooth electron density profile as the electrons are pushed inward by the laser is included self-consistently. It is shown that the JxB heating includes two distinct coupling processes depending on the initial laser and plasma conditions: for a moderate intensity (a <= 1), the ponderomotive force of the laser light can drive a large plasma wave at the point n(e)=4 gamma(0)n(c) resonantly. When this plasma wave is damped, the energy is transferred to the plasma. At higher intensity, the electron density is steepened to a high level by the time-independent ponderomotive force, n(e)> 4 gamma(0)n(c), so that no 2 omega resonance will occur, but the longitudinal component of the oscillating ponderomotive field can lead to an absorption mechanism similar to "vacuum heating." (c) 2006 American Institute of Physics.