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Hemoglobin and serum albumin, two prevalent proteins in human blood, contain unbound cysteine thiol moieties, creating a nucleophilic site with the potential for covalent modification by reactive chemical species. These covalent modifications, called “adducts”, are stable entities that accumulate during acute and chronic exposure and remain covalently bound for the life-span of the protein. Despite their current use as exposure markers for a variety of compounds, the use of adducts in assessing exposure to drugs of abuse has not yet been explored. The goal of this work was to examine the in vitro adduct forming capability of selected drugs of abuse with hemoglobin to provide additional proof of principle for the development of a real-world detection and monitoring analysis method. This goal was accomplished by first analyzing the binding capabilities of the drugs of interest with glutathione, a smaller tripeptide. Use of protein adducts as biomarkers of drug exposure may allow for an increased window of detection, from several days to several months, as compared to current blood analysis methods. In total, there were 16 drugs analyzed in the research, and they covered a wide range of abused drugs, including cocaine, methamphetamine, and Δ 9 -THC. Results from the glutathione trials showed that 10 of the 16 the drugs of interest were able to form covalent adducts with the free thiol moiety, with four drugs forming more than one novel adduct. The MS results for hemoglobin showed 11 adducts formed for five of the drugs under investigation. Additional MS/MS confirmatory data was obtained for two of those 11 adducts. I successfully identifyied adducts formed between drugs of abuse and glutathione and hemoglobin, which have the potential to be used as long-term biomarkers of exposure.

The hydration of propylene to isopropanol was investigated. The first part of this study concerned the direct hydration reaction in various liquid phase systems in the presence of sulfuric acid or p-toluenesulfonic acid. The second part in a two-stage process in which propylene was contacted with excess acetic acid to form isopropyl acetate; the ester was then hydrolyzed to isopropyl alcohol and acetic acid.

This report discusses research involving the fluoroalkoxylation of 2-arylprop-1-en-3-yltrimethylammonium iodides and the useful synthetic application of the adducts formed. The present work includes: 1) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with the sodium salt of 2,2,2-trifluoroethanol; 2) reactions of several fluoroalkoxy alcohols with 2-(4-bromophenyl)prop-1-en-3-yltrimethylammonium iodide; and 3) the oxidation of 2-(4-chlorophenyl)-3-(2,2,2-trifluoroethyoxy)-1-propene using the Lemieux/von Rudloff reagent. This report reveals the experimental conditions and procedures used as well as spectral and physical data of all new compounds synthesized. Explanation is offered for a possible mechanism for the formation of these compounds and recommendations for future research are given.

This report discusses research involving the preparation of germinal difluorodienes. Free radical addition of dibromodifluoromethane to 1-hexene and cyclohexene was performed, followed by a double dehydrohalogenation to yield 1,1-difluoro-1,3-heptadiene and 3-(difluoromethylene)cyclohexene, respectively. NMR, IR, and mass spectral data were obtained and presented as groundwork for further research. A study comparing the free radical initiators, benzoyl peroxide and 2,2’-azobis-(2-methyl)proprionitrile (AIBN) was included, showing neither as ideal initiators for the free radical additions performed. The relative stabilities of the bromodifluoromethyl and the difluoroiodomethyl radicals were approximated. A Diels-Alder reaction of 1,1-difluoro-1,3-heptadiene with 4-phenyl-1,2,4-triazoline-3,5-dione produced the expected [4 + 2] cycloadduct in good yield.

There are many different types of targeted therapy for cancer treatment. The method of light mediated targeted therapy that we have developed uses photocaged molecules and photoswitchable peptides. In photocaging, a biologically active molecule is made inactive by the attachment of a photocleavable blocking group. On exposure to UV radiation the photocleavable entity is removed and the biologically active molecule is released. Using this concept we have designed a prodrug that consists of a cell impermeable hydrophilic molecule attached to a photocaged doxorubicin. Upon irradiation with UV light the photosensitive group is removed and cytotoxic doxorubicin is released at the tumor site. This concept has been further modified by attaching receptor binding molecules to the photocaged entity to increase its specificity. A peptide which consists of an azobenzene photoswitch has been used which, in the dark state is randomly coiled and cell impermeable but upon illumination becomes helical and cell permeable and can be used to deliver drugs into the cells. Upon illumination with UV light of suitable wavelength the azobenzene linker will change from a trans to a cis form and this will convert the randomly coiled cell impermeable peptide into an α helical permeable form. Thus a series of peptides have been designed with different arginine mutations which develop an arginine patch in the helical form. This arginine patch would help in cell permeability by interacting with cell surface glycans. The method could potentially be used to deliver drugs into cells in presence of light.

A thorough understanding of the underlying electronic principles guiding the stability and reactivity of clusters has direct implications for the identification of stable clusters for incorporation into clusters-assembled materials with tunable properties. This work explores the electronic principles governing the stability and reactivity of two types of clusters: ligated metal clusters and silicon encapsulated transition metal clusters. In the first case, the reactivity of iodine-protected aluminum clusters, Al13Ix- (x=0-4) and Al14Iy- (y-0-5), with the protic species methanol was studied. The symmetrical ground states of Al13Ix- showed no reactivity with methanol but reactivity was achieved in a higher energy isomer of Al13I2- with iodines on adjacent aluminum atoms – complementary Lewis acid-base active sites were induced on the opposite side of the cluster capable of breaking the O-H bond in methanol. Al14Iy- (y=2-5) react with methanol, but only at the ligated adatom site. Reaction of methanol with Al14- and Al14I- showed that ligation of the adatom was necessary for the reaction to occur there – revealing the concept of a ligand-activated adatom. In the second case, the study focused heavily on CrSi12, a silicon encapsulated transition metal cluster whose stability and the reason for that stability has been debated heavily in the literature. Calculations of the energetic properties of CrSin (n=6-16) revealed both CrSi12 and CrSi14 to have enhanced stability relative to other clusters; however CrSi12 lacks all the traditional markers of a magic cluster. Molecular orbital analysis of each of these clusters showed the CNFEG model to be inadequate in describing their stability. Because the 3dz2 orbital of Cr is unfilled in CrSi12, this cluster has only 16 effective valence electrons, meaning that the 18-electron rule is not applicable. The moderate stability of CrSi12 can be accounted for by the crystal-field splitting of the 3d orbitals, which pushes the 3dz2 orbital up in energy. CrSi14, on the other hand, has 18 effective valence electrons on Cr, minimal 3d-orbital splitting, and does follow the 18-electron rule. A repetition of these calculations with WSin (n=6-16) showed similar results, except WSi12 shows all the markers of a magic cluster, due to the greater crystal-field splitting of 5d orbitals.

Denna forskningsrapport fokuserar på gymnasieskolans laborationer i kemi och hur dessa förändrats under de senaste 10-20 åren. Motivet till att studera detta är ambitionen att få ökad didaktisk förståelse för laborationen som viktigt inslag i kemiundervisningen. I ett större perspektiv kan detta vara av intresse för att analysera om förändringar av gymnasieskolans kemilaborationer kan utgöra en delförklaring till att svenska universitet upplever ett minskat söktryck för kemi på högskolenivå och om delförklaring kan finnas för att Sverige som nation inte når samma resultat i naturvetenskap som vissa andra länder i internationella kunskapsmätningar. Sex erfarna lärare från sex olika skolor har intervjuats om sina upplevelser av kemilaborationen och vad som påverkat dess utveckling. Ramfaktorteorin har varit grundläggande för detta arbete och som analysmetod har fenomenografin valts. Resultaten visar på en stor variation i vad lärare anser påverkat kemilaborationens förändring. Ökat medvetande och högre krav från lagar och förordningar inom säkerhetsområdet samt att lärare upplever sig ha mindre tillgänglig tid för laborationerna framstår som de tydligaste orsakerna till gjorda förändringar. Även kompensation för försämrade praktiska färdigheter hos elever som lämnar grundskolan framkommer som en bakomliggande faktor. Den nya läroplanen Gy 2011, kostnadsöverväganden och kemi­lokalernas beskaffenhet framkom som mindre avgörande för kemilaborationens utveckling.

The so-called "lime-induced" chlorosis has been recognized for many years as a problem where plants are grown on calcareous soils. The characteristics associated with lime-induced chlorosis are the same as those associated with iron deficiency chlorosis--interveinal yellowing of the leaves at the meristemic region combined with reduced vigor of the plant as a whole. Lime-induced chlorosis is unique in that the iron content of both chlorotic plant and the soil do not always show a deficiency in iron when chemically analyzed. This leads to the theory that iron is inactivated in both the soil and plant. Although no single factor has been found to adequately explain this physiological disease, many factors have been associated with it. Thorne, Wann, and Robinson (1950) observed that calcareous soils characterized by fine texture, high moisture content, poor aeration, and cool temperatures intensify the development of chlorosis in plants. In general increased chlorosis has also been noted under conditions of high pH. The pH and phosphorus effects appear to involve reduced iron solubility in the soil and within the plant while the exact effects of the bicarbonate ion on chlorosis have not been established.

Soil-phosphorus relations have attracted the interest of many investigators since Liebig introduced his famous theory about the importance of the mineral matters to the plant in 1840. It was soon realized that phosphorus nutrition was a problem not easily solved for two reasons. 1. The added phosphorus fertilizers, soon after soil application are converted by some reactions in the soil to complex compounds far less soluble, consequently less available to the plant. Conclusions about this process led to controversial debates until it was discovered that a general statement covering all soils was impossible since the reactions involved in each case are different. 2. There was confusion caused by the use of two terms coined to express the plant's need for phosphorus. The first term, soluble phosphorus, was based on the assumption that nutrient absorption is a simple diffusion of ions from the soil solution into the roots while the second term, available phosphorus, was based on the observation that the plant absorbed more than that which could be estimated as soluble phosphorus from some insoluble sources. A general definition was given to the term available phosphorus as "that part of soil phosphorus which may be absorbed by ordinary crop plant in the production of plant substance." Later some restrictions were applied to regard the physical conditions of both soils and plants.