The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, Literature Review, TR-480, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

The Deleterious Chemical Effects of Concentrated Deicing Solutions on Portland Cement Concrete, Technical Appendices, TR-480, 2008

This research project investigated the effects of concentrated brines of magnesium chloride, calcium chloride, sodium chloride, and calcium magnesium acetate on portland cement concrete. Although known to be effective at deicing and anti-icing, the deleterious effects these chemicals may have on concrete have not been well documented. As a result of this research, it was determined that there is significant evidence that magnesium chloride and calcium chloride chemically interact with hardened portland cement paste in concrete resulting in expansive cracking, increased permeability, and a significant loss in compressive strength. Although the same effects were not seen with sodium chloride brines, it was shown that sodium chloride brines have the highest rate of ingress into hardened concrete. This latter fact is significant with respect to corrosion of embedded steel. The mechanism for attack of hardened cement paste varies with deicer chemical but in general, a chemical reaction between chlorides and cement hydration products results in the dissolution of the hardened cement paste and formation of oxychloride phases, which are expansive. The chemical attack of the hardened cement paste is significantly reduced if supplementary cementitious materials are included in the concrete mixture. Both coal fly ash and ground granulated blast furnace slag were found to be effective at mitigating the chemical attack caused by the deicers tested. In the tests performed, ground granulated blast furnace slag performed better as a mitigation strategy as compared to coal fly ash. Additionally, siloxane and silane sealants were effective at slowing the ingress of deicing chemicals into the concrete and thereby reducing the observed distress. In general, the siloxane sealant appeared to be more effective than the silane, but both were effective and should be considered as a maintenance strategy.

Maintenance and Design of Steel Abutment Piles in Iowa Bridges, TR-622, 2014

Soil consolidation and erosion caused by roadway runoff have exposed the upper portions of steel piles at the abutments of numerous bridges, leaving them susceptible to accelerated corrosion rates due to the abundance of moisture, oxygen, and chlorides at these locations. This problem is compounded by the relative inaccessibility of abutment piles for close-up inspection and repair. The objective of this study was to provide bridge owners with recommendations for effective methods of addressing corrosion of steel abutment piles in existing and future bridges A review of available literature on the performance and protection of steel piles exposed to a variety of environments was performed. Eight potential coating systems for use in protecting existing and/or new piles were selected and subjected to accelerated corrosion conditions in the laboratory. Two surface preparation methods were evaluated in the field and three coating systems were installed on three piles at an existing bridge where abutment piles had been exposed by erosion. In addition, a passive cathodic protection (CP) system using sacrificial zinc anodes was tested in the laboratory. Several trial flowable mortar mixes were evaluated for use in conjunction with the CP system. For existing abutment piles, application of a protective coating system is a promising method of mitigating corrosion. Based on its excellent performance in accelerated corrosion conditions in the laboratory on steel test specimens with SSPC-SP3, -SP6, and -SP10 surface preparations, glass flake polyester is recommended for use on existing piles. An alternative is epoxy over organic zinc rich primer. Surface preparation of existing piles should include abrasive blast cleaning to SSPC-SP6. Although additional field testing is needed, based on the results of the laboratory testing, a passive CP system could provide an effective means of protecting piles in existing bridges when combined with a pumped mortar used to fill voids between the abutment footing and soil. The addition of a corrosion inhibitor to the mortar appears to be beneficial. For new construction, shop application of thermally sprayed aluminum or glass flake polyester to the upper portion of the piles is recommended.

Organic geochemistry of Jurassic-Cretaceous source rocks and oil seeps from the profile across the Adriatic-Dinaric carbonate platform

Organic geochemical and stable isotope investigations were performed to provide an insight into the depositional environments, origin and maturity of the organic matter in Jurassic and Cretaceous formations of the External Dinarides. A correlation is made among various parameters acquired from Rock-Eval, gas chromatography-mass spectrometry data and isotope analysis of carbonates and kerogen. Three groups of samples were analysed. The first group includes source rocks derived from Lower Jurassic limestone and Upper Jurassic ``Leme'' beds, the second from Upper Cretaceous carbonates, while the third group comprises oil seeps genetically connected with Upper Cretaceous source rocks. The carbon and oxygen isotopic ratios of all the carbonates display marine isotopic composition. Rock-Eval data and maturity parameter values derived from biomarkers define the organic matter of the Upper Cretaceous carbonates as Type I-S and Type II-S kerogen at the low stage of maturity up to entering the oil-generating window. Lower and Upper Jurassic source rocks contain early mature Type III mixed with Type IV organic matter. All Jurassic and Cretaceous potential source rock extracts show similarity in triterpane and sterane distribution. The hopane and sterane distribution pattern of the studied oil seeps correspond to those from Cretaceous source rocks. The difference between Cretaceous oil seeps and potential source rock extracts was found in the intensity and distribution of n-alkanes, as well as in the abundance of asphaltenes which is connected to their biodegradation stage. In the Jurassic and Cretaceous potential source rock samples a mixture of aromatic hydrocarbons with their alkyl derivatives were indicated, whereas in the oil seep samples extracts only asphaltenes were observed.

Solid-Phase Synthesis of New Trp(Nps)-Containing Dipeptide Derivatives as TRPV1 Channel Blockers

Trp(Nps)-Lys-NH2 derivatives, bearing alkyl or guanidine groups either at the N-terminus or on the Lys side-chain or at both positions were conveniently prepared on solid-phase and evaluated as TRPV1 channel antagonists.

Laboratory Investigation of Bridge Strip Seal Joint Termination Details, SPR RB08-014, 2016

Bridge expansion joints, if not properly designed, constructed, and maintained, often lead to the deterioration of critical substructure elements. Strip seal expansion joints consisting of a steel extrusion and neoprene gland are one type of expansion joint and are commonly used by the Iowa Department of Transportation (DOT). Strip seal expansion joints are susceptible to tears and pull outs that allow water, chlorides, and debris to infiltrate the joint, and subsequently the bearings below. One area of the strip seal that is particularly problematic is where it terminates at the interface between the deck and the barrier rail. The Iowa DOT has noted that the initial construction quality of the current strip seal termination detail is not satisfactory, nor ideal, and a need exists for re-evaluation and possibly re-design of this detail. Desirable qualities of a strip seal termination detail provide a seal that is simple and fast to construct, facilitate quick gland removal and installation, and provide a reliable, durable barrier to prevent chloride-contaminated water from reaching the substructure. To meet the objectives of this research project, several strip seal termination details were evaluated in the laboratory. Alternate termination details may not only function better than the current Iowa DOT standard, but are also less complicated to construct, facilitating better quality control. However, uncertainties still exist regarding the long-term effects of using straight-through details, with or without the dogleg, that could not be answered in the laboratory in the short time frame of the research project.

Structure of the glycosyl-phosphatidylinositol membrane anchor of the Leishmania major promastigote surface protease.

In common with many other plasma membrane glycoproteins of eukaryotic origin, the promastigote surface protease (PSP) of the protozoan parasite Leishmania contains a glycosyl-phosphatidylinositol (GPI) membrane anchor. The GPI anchor of Leishmania major PSP was purified following proteolysis of the PSP and analyzed by two-dimensional 1H-1H NMR, compositional and methylation linkage analyses, chemical and enzymatic modifications, and amino acid sequencing. From these results, the structure of the GPI-containing peptide was found to be Asp-Gly-Gly-Asn-ethanolamine-PO4-6Man alpha 1-6Man alpha 1-4GlcN alpha 1-6myo-inositol-1-PO4-(1-alkyl-2-acyl-glycerol). The glycan structure is identical to the conserved glycan core regions of the GPI anchor of Trypanosoma brucei variant surface glycoprotein and rat brain Thy-1 antigen, supporting the notion that this portion of GPIs are highly conserved. The phosphatidylinositol moiety of the PSP anchor is unusual, containing a fully saturated, unbranched 1-O-alkyl chain (mainly C24:0) and a mixture of fully saturated unbranched 2-O-acyl chains (C12:0, C14:0, C16:0, and C18:0). This lipid composition differs significantly from those of the GPIs of T. brucei variant surface glycoprotein and mammalian erythrocyte acetylcholinesterase but is similar to that of a family of glycosylated phosphoinositides found uniquely in Leishmania.

Qualitative structure-metabolism relationships in the hydrolysis of carbamates.

The aims of this review were 1) to compile a large number of reliable literature data on the metabolic hydrolysis of medicinal carbamates and 2) to extract from such data a qualitative relation between molecular structure and lability to metabolic hydrolysis. The compounds were classified according to the nature of their substituents (R³OCONR&supl;R²), and a metabolic lability score was calculated for each class. A trend emerged, such that the metabolic lability of carbamates decreased (i.e., their metabolic stability increased), in the following series: Aryl-OCO-NHAlkyl >> Alkyl-OCO-NHAlkyl ~ Alkyl-OCO-N(Alkyl)? ? Alkyl-OCO-N(endocyclic) ? Aryl-OCO-N(Alkyl)? ~ Aryl-OCO-N(endocyclic) ? Alkyl-OCO-NHAryl ~ Alkyl-OCO-NHAcyl?>> Alkyl-OCO-NH? > Cyclic carbamates. This trend should prove useful in the design of carbamates as drugs or prodrugs.

Eräiden paperinvalmistuksessa käytettävien vahadispersioiden stabiilisuuden hallinta

Diplomityön tavoitteena oli selvittää millainen laaduntarkastus AKD-dispersioille tulisi suorittaa kuormien vastaanotossa ja tulisiko dispersioiden laatu tarkastaa uudelleen ennen annostelua. Tätä varten seurattiin toimituserien laadun tasaisuutta ja tarkasteltiin varastointiolosuhteiden vaikutusta dispersioiden säilyvyyteen. Lisäksi kartoitettiin dispersioiden käsittelyssä ja kartonginvalmistusprosessissa esiintyvien riskitekijöiden vaikutuksia kaupallisten dispersioiden stabiilisuuteen. Kirjallisuusosassa perehdyttiin kolloidisiin dispersioihin sekä niiden stabiilisuuteen vaikuttaviin tekijöihin. AKD-dispersiot valmistetaan emulgointitekniikoiden avulla, joten dispergointimenetelmien ohella käsiteltiin myös emulsioiden valmistamista. Lisäksi luotiin katsaus dispersioteknologian tärkeimpiin analyysimenetelmiin. Alkyyliketeenidimeerin osalta käsiteltiin emulgoinnin lisäksi vahan ja muiden lisäaineiden vaikutuksia dispersioiden stabiilisuuteen ja myös niiden merkitystä dispersioiden formuloinnissa. AKD-liimauksen osalta esiin tuotiin AKD:n tärkeimmät reaktiomekanismit, sillä ne liittyvät osittain myös dispersioiden stabiilisuuteen. Lopuksi luotiin lyhyt katsaus AKD-dispersioiden stabiilisuutta käsittelevään tutkimukseen, jota on toistaiseksi julkaistu varsin niukasti. Kokeellisessaosassa tarkastelun kohteeksi valittiin neljä kaupallista alkyyliketeenidimeerinvesidispersiota, joiden koostumus ja ominaisuudet selvitettiin perusteellisesti. Tarkoituksena oli auttaa ymmärtämään dispersioiden stabiilisuudessa mahdollisesti esiintyviä eroja. Laajamittainen dispersioiden karakterisointi näyttää olevan tarpeen ainakin otettaessa uutta AKD-laatua käyttöön, sillä dispersioiden koostumus ja ominaisuudet voivat vaihdella merkittävästi. AKD-dispersioiden laadussa esiintyi vaihtelua eri toimituserien välillä. Suurimmat vaihtelut havaittiin dispersioiden varaustiloissa ja partikkelikokojakaumissa. Laadun epätasaisuuden vuoksi vastaanottotarkastuksen merkitys korostuu. Vastaanottotarkastuksessa syytä olisi kiinnittää dispersion kuiva-ainepitoisuuden ohella sen viskositeettiin, varaustilaan, tehoainepitoisuuteen sekä rakenteeseen. Rakenteen tarkastelussa optinen mikroskooppi voi rutiininomaisessa seurannassa korvata partikkelikokojakauman määrittämisen. Varastointilämpötilan vaikutus dispersioidenlaatuun on merkittävä. Dispersiot säilyvät parhaiten viileässä, joten jos varastosäiliöissä ei ole jäähdytystä, on dispersioiden laadun tarkastus tarpeen myös ennen annostelua. Jotta dispersion kunnosta saadaan luotettava arvio, on viskositeetin määrittämiseen yhdistettävä vähintään rakenteen tarkastelu optisella mikroskoopilla. Mekaaninen rasitus voi dominoivasta stabilointimekanismistariippuen aiheuttaa dispersiossa hienoaineen muodostumista tai partikkelien flokkaantumista. Stabilointimekanismi vaikuttaa niin ikään partikkelien käyttäytymiseen korkeissa lämpötiloissa. Dispersioiden stabiilisuuden todettiin heikkenevän pH:n kohotessa emäksiselle alueelle. Elektrolyyttikonsentraatio vaikuttaa partikkelien mikroelektroforeettiseen ioniliikkuvuuteen merkittävästi. Kartonkikoneen märkäosan kemikaaleista anionisen retentioaineen (BMA) todettiin vuorovaikuttavan kationisten AKD-partikkelien kanssa selvimmin. Mikroelektroforeettisen ioniliikkuvuuden mittaaminen kiertovedessä todettiin tärkeäksi, sillä se kuvaa dispersion käyttäytymistä sen käyttöympäristössä.

pH Sensitive surfactants from lysine: assessment of their cytotoxicity and environmental behavior

The toxicity and environmental behavior of new pH-sensitive surfactants from lysine are presented. Three different chemical structures are studied: surfactants with one amino acid and one alkyl chain, surfactants with two amino acids on the polar head and one alkyl chain, and gemini surfactants. The pH sensitivity of these compounds can be tuned by modifying their chemical structures. Cytotoxicity has been evaluated using erythrocytes and fibroblast cells. The toxic effects against these cells depend on the hydrophobicity of the molecules as well as their cationic charge density. The effect of hydrophobicity and cationic charge density on toxicity is different for each type of cells. For erythrocytes, the toxicity increases as hydrophobicity and charge density increases. Nevertheless, for fibroblasts cationic charge density affects cytotoxicity in the opposite way: the higher charge density, the lower the toxicity. The effect of the pH on hemolysis has been evaluated in detail. The aquatic toxicity was established using Daphnia magna. All surfactants yielded EC50 values considerably higher than that reported for cationic surfactants based on quaternary ammonium groups. Finally, their biodegradability was evaluated using the CO2 headspace test (ISO 14593). These lysine derivatives showed high levels of biodegradation under aerobic conditions and can be classified as"readily biodegradable compounds".

Four-hour infusions of synthetic atrial natriuretic peptide in normal volunteers.

Two doses of synthetic atrial natriuretic peptide (0.5 and 5.0 micrograms/min) and its vehicle were infused intravenously for 4 hours in eight salt-loaded normal volunteers, and the effect on blood pressure, heart rate, renal hemodynamics, solute excretion, and secretion of vasoactive hormones was studied. The 0.5 micrograms/min infusion did not alter blood pressure or heart rate, whereas the 5.0 micrograms/min infusion significantly reduced the mean pressure by 20/9 mm Hg after 2.5 to 3 hours and increased the heart rate slightly. Inulin clearance was not significantly changed, but the mean p-aminohippurate clearance fell by 13 and 32% with the lower and higher doses, respectively. Urinary excretion of sodium and chloride increased slightly with the lower dose. With the higher dose, a marked increase in urinary excretion of sodium, chloride, and calcium was observed, reaching a peak during the second hour of the infusion. Potassium and phosphate excretion did not change significantly. A brisk increase in urine flow rate and fractional water excretion was seen only during the first hour of the high-dose infusion. Signs and symptoms of hypotension were observed in two subjects. No change in plasma renin activity, angiotensin II, or aldosterone was observed during either infusion, but a marked increase occurred after discontinuation of the high-dose infusion. In conclusion, the 5 micrograms/min infusion induced a transient diuretic effect, delayed maximal natriuretic activity, and a late fall in blood pressure, with no change in inulin clearance but a dose-related decrease in p-aminohippurate clearance. Despite large amounts of sodium excreted and blood pressure reduction, no counterregulatory changes were observed in the renin-angiotensin-aldosterone system or plasma vasopressin levels during the infusion.

The use of branched ketenedimers in solving the deposit problems related to the internal sizing of uncoated fine paper

Alkyl ketene dimers (AKD) are effective and highly hydrophobic sizing agents for the internal sizing of alkaline papers, but in some cases they may form deposits on paper machines and copiers. In addition, alkenyl succinic anhydrides (ASA)- based sizing agents are highly reactive, producing on-machine sizing, but under uncontrolled wet end conditions the hydrolysis of ASA may cause problems. This thesis aims at developing an improved ketene dimer based sizing agent that would have a lower deposit formation tendency on paper machines and copiers than a traditional type of AKD. The aim is also to improve the ink jet printability of a AKD sized paper. The sizing characteristics ofketene dimers have been compared to those of ASA. A lower tendency of ketene dimer deposit formation was shown in paper machine trials and in printability tests when branched fatty acids were used in the manufacture of a ketene dimer basedsizing agent. Fitting the melting and solidification temperature of a ketene dimer size to the process temperature of a paper machine or a copier contributes to machine cleanliness. A lower hydrophobicity of the paper sized with branched ketene dimer compared to the paper sized with traditional AKD was discovered. However, the ink jet print quality could be improved by the use of a branched ketene dimer. The branched ketene dimer helps in balancing the paper hydrophobicity for both black and color printing. The use of a high amount of protective colloidin the emulsification was considered to be useful for the sizing performance ofthe liquid type of sizing agents. Similar findings were indicated for both the branched ketene dimer and ASA.

Phospholipid bilayer perturbing-properties underlying lysis induced by pH-sensitive cationic lysine-based surfactants in biomembranes

Many strategies for treating diseases require the delivery of drugs into the cell cytoplasm following internalization within endosomal vesicles. Thus, compounds triggered by low pH to disrupt membranes and release endosomal contents into the cytosol are of particular interest. Here, we report novel cationic lysine-based surfactants (hydrochloride salts of Nε- and Nα-acyl lysine methyl ester) that differ in the position of the positive charge and the length of the alkyl chain. Amino acid-based surfactants could be promising novel biomaterials in drug delivery systems, given their biocompatible properties and low cytotoxic potential. We examined their ability to disrupt the cell membrane in a range of pH values, concentrations and incubation times, using a standard hemolysis assay as a model of endosomal membranes. Furthermore, we addressed the mechanism of surfactant-mediated membrane destabilization, including the effects of each surfactant on erythrocyte morphology as a function of pH. We found that only surfactants with the positive charge on the α-amino group of lysine showed pH-sensitive hemolytic activity and improved kinetics within the endosomal pH range, indicating that the positive charge position is critical for pH-responsive behavior. Moreover, our results showed that an increase in the alkyl chain length from 14 to 16 carbon atoms was associated with a lower ability to disrupt cell membranes. Knowledge on modulating surfactant-lipid bilayer interactions may help us to develop more efficient biocompatible amino acid-based drug delivery devices.

Uuttoprosessin suunnittelu

Teknologian kehitys ja prosessien tiukempi valvonta ovat alentaneet selluteollisuuden häviöitä tehden prosesseista suljetumpia. Valitettavasti nämä edistysaskeleet teknologiassa ovat lisänneet prosessiin kuulumattomien yhdisteiden määrää kemikaalien talteenottokierrossa. Näistä kemikaaleista haitallisimpia ovat kloridi- ja kaliumyhdisteet, jotka tulevat prosessiin raaka-aineiden ja prosessikemikaalien mukana. Kloridi ja kalium muodostavat emäksisissä liuoksissa epäorgaanisia liukoisia yhdisteitä, jotka rikastuvat lipeäkiertoon. Soodakattilassa kloridien läsnäolo alentaa tuhkan sulamislämpötilaa sekä tarttumispistettä, lisää korroosiota ja saostumien muodostumista kattilan pinnalle. Nämä seuraukset voivat vähentää vuosituotantoa ja nostaa korjauskustannuksia. Kaliumin ja kloridin rikastumista talteenottokiertoon voidaan estää poistamalla ne prosessista. Prosessiin kuulumattomat yhdisteet tulisi poistaa talteenottoprosessista ja säilyttää samalla korkea kemikaalien talteenottoprosentti. Koska kaliumin ja kloridin rikastumiskertoimet soodakattilan tuhkassa ovat korkeita, on tuhkan käsittely tehokasta. Kloridin ja kaliumin poistoon on kehitetty menetelmiä, joilla voidaan vähentää hyödyllisten kemikaalien häviöitä. Näitä menetelmiä ovat uutto, ioninvaihto, elektrodialyysi, jäähdytyskiteytys ja haihdutuskiteytys. Menetelmissä tuhka jaetaan kloridi- ja kaliumpitoiseen osaan ja natriumsulfaattipitoiseen osaan. Kloridi ja kalium poistetaan prosessista ja loput palautetaan lipeäkiertoon. Kloridin ja kaliumin poistoa tuhkasta tutkittiin uuttamalla tuhkaa vedellä. Parhaissa käyttöolosuhteissa natriumsulfaatin liukoisuus veteen on huomattavasti alhaisempi kuin kaliumkloridin liukoisuus veteen. Optimaalinen uuttolämpötila ja tuhka-vesisuhde määritettiin siten, että kloridi- ja kaliumpitoisuudet suodoksessa olivat mahdollisimman korkeat sekä natriumin ja muiden anioneiden pitoisuudet suodoksessa mahdollisimman alhaiset. Saatuja tuloksia käytettiin jatkuvatoimisen uuttoprosessin suunnittelussa.

Cell wall precursors are required to organize the chlamydial division septum.

Members of the Chlamydiales order are major bacterial pathogens that divide at mid-cell, without a sequence homologue of the FtsZ cytokinetic tubulin and without a classical peptidoglycan cell wall. Moreover, the spatiotemporal mechanisms directing constriction in Chlamydia are not known. Here we show that the MreB actin homologue and its conserved regulator RodZ localize to the division furrow in Waddlia chondrophila, a member of the Chlamydiales order implicated in human miscarriage. RodZ is recruited to the septal site earlier than MreB and in a manner that depends on biosynthesis of the peptidoglycan precursor lipid II by the MurA enzyme. By contrast, crosslinking of lipid II peptides by the Pbp3 transpeptidase disperses RodZ from the septum. Altogether, these findings provide a cytological framework for understanding chlamydial cytokinesis driven by septal cell wall synthesis.