Santrauka Tyrimas atliktas Lietuvos Sveikatos Mokslų Universitete, šio tyrimo duomenys surinkti iš veterinarijos klinikos „Veterinarinės Medicinos Centras“, 2011 – 2013 metų laikotarpiu. Darbo apimtis 30 puslapių, kuriuose yra 1 lentelė ir 10 diagramų. Darbo tikslas buvo išnagrinėti šunų susirgimo šlapimo takų akmenlige 2011 – 2013 metais sergamumą. Tiriamojo darbo uždaviniai buvo suformuluoti norint nustatyti šlapimo takų akmenligės pasireiškimo dažnumą, priklausomai nuo kitų urogenitalinės sistemos sutrikimo atvejų; kokių tipų akmenys ir/ar kristalai buvo nustatyti tyrimo eigoje, bei susidariusių susirgimų priklausomybę nuo amžiaus, lyties bei veislės. Išanalizavus 138 ligos istorijas susijusias su urogenitalinės sistemos problemomis, buvo nustatyti 47 (34,058%) šlapimo takų akmenligės atvejai. Visi sergantieji buvo išskirstyti į keletą skirtingų grupių, remiantis trimis pagrindiniais skirtumais: lytis, amžius ir veislė. Grupės skirstomos: I) pagal lytį, patelės (n=21) ir patinėliai (n=26); II) pagal amžių, buvo sudarytos keturios grupės: nuo 0 iki 3 metų (n=12), nuo 4 iki 6 metų (n=17), nuo 7 iki 10 metų (n=17) ir virš 11 metų (n=1); III) pagal veislę, buvo išskirstyta į dvi pagrindines grupes 1) grynakraujai (n=38), 22 skirtingos veislės ir 2) mišrūnai šunys (n=9). Apibendrinus tyrimo metu gautus rezultatus buvo padaryta išvada, kad šlapimo takų akmenligė pasireiškė 34,058% pacientams, iš visų susirgimų šlapimo sistemos ligomis. Iš visų tiriamųjų gausiausiai sirgo... [toliau žr. visą tekstą] / Summury The study was fufilled at Lithuanian University of Health Sciences , the study material collected from the veterinary clinic „Veterinarės Medicinos Centras“, time period of 2011 – 2013 years. Thesis volume of 30 pages, containing 1 table and 10 figure. The aim was to examine the canine urolithiasis morbidity in 2011 - 2013 years . Research work tasks have been formulated to identify urinary tract stones , depending on the frequency of occurrence of other urogenital system disruptions , what types of stones and/or crystals have been identified during the course of the study , and the resulting onset of age, sex and breed. An analysis of 138 case histories associated with urogenital problems were identified 47 ( 34,058%) of urolithiasis cases . All the patients were broken down into several different groups based on the three main differences: gender , age and breed . Sets are : I) according to gender, females ( n = 21 ) and males ( n = 26 ), II ) according to age, was formed four groups : 0 to 3 years ( n = 12) from 4 to 6 years of age ( n = 17 ) , from 7 to 10 years ( n = 17 ) and over 11 years ( n = 1 ) and III) according to the breed was split into two main groups 1 ) pure breed ( n = 38 ) , 22 different varieties and 2 ) mixed breed dogs ( n = 9). Summarizing the research results , it was concluded that urolithiasis patients experienced 34,058 % of all patients with urinary system diseases. Among the most heavily suffered from 80.851 % pure breed dogs ( p < 0.001 )... [to full text]

Bibliography :leaves 149-172. / vii, 172,[60] leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / The investigations centre on the use of [beta]-aminothiols (cysteine, cysteamine and penicillamine) to decrease endogenous oxalate production by forming adducts with glyoxylate, the immediate precursor of oxalate. They indicate that cysteine delivery drugs like OTC have the potential to aid in management of calcium oxalate stone disease, thereby reducing endogenous oxalate production and urinary oxalate excretion. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physiology, 1995?

This thesis deals with certain aspects of the solution chemistry of the simple dicarboxylate anions: oxalate, malonate and succinate, up to high concentrations. These ions are either significant impurities in the concentrated alkaline aluminate solutions used in the Bayer process for the purification of alumina, or are useful models for degraded organic matter in industrial Bayer liquors. Such impurities are known to have important effects on the operation of the Bayer process. To develop a better understanding of the speciation of oxalate (the major organic impurity in Bayer liquors) in concentrated electrolyte solutions, the formation constant (Log£]) of the extremely weak ion pair formed between sodium (Na+) and oxalate (Ox2ƒ{) ions was determined at 25 oC as a function if ionic strength in TMACl media by titration using a Na+ ion selective electrode. Attempts to measure this constant in CsCl media were unsuccessful probably because of competition for Ox2ƒ{ by Cs+. Aqueous solutions of sodium malonate (Na2Mal) and sodium succinate (Na2Suc) were studied up to high (saturation) concentrations at 25 oC by dielectric relaxation spectroscopy (DRS) over the approximate frequency range 0.1 „T £h/GHz „T 89. To complement a previous study of Na2Ox, formation constants of the Na+-dicarboxylate ion pairs were determined and they were shown to be of the solvent-shared type. Both the Mal2ƒ{ and Suc2ƒ{ ions, in contrast to Ox2ƒ{, were also shown to possess large secondary hydration shells Apparent molal volumes (Vf) and heat capacities at constant pressure (Cpf) of aqueous solutions of Na2Ox, Na2Suc, Na2Mal and K2Ox were determined at 25 oC up to their saturation limits using vibrating tube densitometry and flow calorimetry. These data were fitted using a Pitzer model. The adherence of Vf and Cpf of various Na+ and K+ salts to Young¡¦s rule was examined up to high concentrations using the present and literature data. Young¡¦s rule was then used to estimate hypothetical values of Cpf and Vf for the sparingly soluble Na2Ox at high ionic strengths, which are required for the thermodynamic modelling of Bayer liquors. The solubility of Na2Ox in various concentrated electrolytes was measured, at temperatures from 25 oC to 70 oC in media both with (NaCl, NaClO4, NaOH) and without a common ion (KCl, CsCl, TMACl). The common ion effect was found to dominate the solubility of Na2Ox. The solubility of calcium oxalate monohydrate (CaOx„ªH2O) was also determined. The solubilities of both Na2Ox and CaOx„ªH2O in media without a common ion increased with increasing electrolyte concentration, except in TMACl media, where they decreased. The solubility of Na2Ox was modelled using a Pitzer model assuming the Pitzer parameters for Na2SO4 and minimising the free energy of the system. The data were modelled successfully over the full concentration and temperature range of all the electrolytes, including ternary (mixed electrolyte) solutions.

Μελετάται η ανάπτυξη μεθόδου για την εις βάθος συσσωμάτωση χαλαρών εδαφών που προορίζονται για οικοδόμηση καθώς και για εδάφη περιοχών που υποφέρουν από κατολισθήσεις. Με την ίδια κατά βάση μεθοδολογία, επιχειρείται η επίτευξη στεγανοποίησης κατασκευών σκυροδέματος που υποφέρουν από διαρροές ή από υγρασία και είναι αναγκαία η άμεση αποκατάσταση τους με χαμηλό κόστος. Και στις δύο περιπτώσεις η νέα μεθοδολογία αποτελεί καινοτομία φιλική στο περιβάλλον. Για το σκοπό αυτό προτάθηκε ένα σύστημα υδατοδιαλυτών χημικών με σκοπό την επί τόπου καταβύθιση ενός δυσδιάλυτου άλατος στα τοιχώματα των πόρων του σκυροδέματος και την μείωση της υδατοπερατότητας του υλικού. Το προτεινόμενο άλας ήταν το οξαλικό ασβέστιο (CaC2O4). Το οξαλικό ασβέστιο είναι το κύριο συστατικό των λίθων του ουροποιητικού. Το μονοένυδρο και διένυδρο οξαλικό ασβέστιο έχουν ανιχνευθεί στην πατίνα, το επιφανειακό επίστρωμα που έχει σχηματιστεί σε αρχαία μνημεία, αγάλματα και φυσικά σχηματισμένους βράχους. Μέχρι σήμερα θεωρείται ότι το στρώμα αυτό οξαλικού ασβεστίου στην επιφάνεια των αρχαίων μνημείων, παίζει σημαντικό προστατευτικό ρόλο για την επιφάνεια που καλύπτει. Αρχικά έγινε συστηματική μελέτη της αυθόρμητης καταβύθισης του οξαλικού ασβεστίου σε αντιδραστήρες διαλείποντος έργου. Οι πειραματικές συνθήκες ήταν τέτοιες που να προσομοιάζουν τις συνθήκες κατά την εφαρμογή των χημικών στο σκυρόδεμα (θερμοκρασία 25°C, pH=6.5 και 10). Μελετήθηκε η επίδραση συνθετικών κρυστάλλων μονοένυδρου οξαλικού ασβεστίου (COM) και κόκκων τσιμεντοκονιάματος. Σε όλες τις περιπτώσεις ανιχνεύθηκε το COM στην καταβυθιζόμενη φάση. Οι κρύσταλλοι αναπτύσσονται πάνω στους κόκκους τους τσιμεντοκονιάματος και σχηματίζουν μεγάλα συσσωματώματα. Το μέγεθός τους (8-10 μm) και το σχήμα τους (εξαγωνικό πρισματικό) είναι χαρακτηριστικά που ευνοούν το οξαλικό ασβέστιο να παίξει το ρόλο συνδετικού υλικού σε πορώδη μέσα. Ο κύριος μηχανισμός κρυσταλλικής ανάπτυξης είναι η επιφανειακή διάχυση των δομικών μονάδων στην επιφάνεια του κρυστάλλου. Τέλος, μελετήθηκε η επί τόπου καταβύθιση του COM σε δοκίμια τσιμεντοκονιάματος. Τα διαλύματα εισέρχονταν στο εσωτερικό του δοκιμίου με τη βοήθεια της βαρύτητας. Στα δοκίμια τσιμεντοκονιάματος πραγματοποιήθηκαν πειράματα τριχοειδούς εισρόφησης νερού και μηχανικής επιφανειακής απότριψης. Κατεργασία του τσιμεντοκονιάματος με διάλυμα οξαλικού νατρίου σε υψηλές θερμοκρασίες, φαίνεται να μειώνει την εισρόφηση του νερού. / A new environmental friendly method, for the stabilization of loose soils to be used as building sites and for the amelioration of the properties of concrete constructions suffering from water leaks or humidity has been developed. The novelty of the proposed method is lying on the in situ precipitation of calcium oxalate monohydrate (COM) within the porous structure of soil or on the pore walls of the construction material (concrete) in order to minimize water leakage. Calcium oxalate, encountered often in kidney stones in the form of COM, is notorious for the formation of hard, non-porous aggregates which adhere tenaciously onto substrates. Calcium oxalate in the form of a protective patina is often met as surface layer in marbles or limestones. Mechanistic information concerning the formation of COM in supersaturated solutions may be obtained in seeded growth experiments. In these experiments, supersaturated solutions are seeded either with seed crystals of the same under investigation salt or of any other insoluble solid material on which the heterogeneous formation of the salt of interest may take place. Among the objectives of the present work was to investigate the role of concrete grains on the nucleation and crystal growth of COM. The analysis of the kinetics data showed that the prevalent mechanism for COM precipitation was surface diffusion. In all cases the only crystalline phase forming in the supersaturated solutions was identified as COM. In the second part of the present work the in situ precipitation of COM into mortar samples was studied. SEM analysis showed that crystallization indeed took place within the pores of the concrete. Best results in terms of waterproofing of concrete material were obtained in the case of treating concrete surfaces with sodium oxalate solution at high temperature.

Oxaliplatin is an anticancer drug widely used in cancer chemotherapy. This thesis evaluates whether a specific dose-banding scheme for oxaliplatin could replace the individual dosing method that is currently used in the oxaliplatin administration. Dose-banding was introduced into UK clinical practice in 2001, as it reduces delays in patients receiving their treatment and, through quality control and end-product testing, safeguards the infusion quality and patient safety. A range of studies were included in this thesis: an extended stability study on oxaliplatin infusions using a sequential temperature cycling design; studies on oxalate, a potential degradation product and metabolite of oxaliplatin which has been linked to oxaliplatin neurotoxicity and the development of an ex vivo pharmacokinetic (PK) simulation model to compare the effect of different oxaliplatin dosing methods on its therapeutic outcomes. The shelf-life of oxaliplatin infusions over a concentration range of 0.2 mg/mL – 0.7 mg/mL is extended to 84 days when stored at 2 – 8℃ plus a further 7 days after being left at room temperature (25℃) for 24 hours. This ensures the unused oxaliplatin infusions are safe to be re-issued to patients, which could reduce drug wastage. The oxalate study suggests that the dose-limiting neurotoxicity of oxaliplatin is unlikely to be directly related to the oxalate produced from oxaliplatin degradation in infusions or from the non-enzymic transformation of oxaliplatin in vivo because the oxalate levels from these routes are minor compared to the endogenous level. The safety and efficacy of dose-banding schemes was demonstrated by comparing the simulated PK characteristics gained from the ex vivo model. Dose-banding with the +10% maximum deviation was selected as the most promising dosing scheme for oxaliplatin. Finally, recommendations are made concerning the introduction of oxaliplatin dose-banding scheme into clinical practice, and on the benefits of harmonised dose-banding schemes.

Metal ions play essential roles in biological functions including catalysis, protein stability, DNA-protein interactions and cell signaling. It is estimated that 30% of proteins utilize metals in some fashion. Additionally, methods by which metal ions can be visualized have been utilized to study metal concentrations and localizations in relation to disease. Understanding the roles metals play in biological systems has great potential in medicine and technology. Chapters 1 and 2 of this dissertation analyzes the structure and function of the Mn-dependent enzyme oxalate decarboxylase (OxDc) and Chapter 2 presents a bioinformatic analysis of the cupin superfamily that provides the structural scaffold of the decarboxylase. The X-ray crystal structure of the W132F variant was determined and utilized together with EPR data to develop a computational approach to determining EPR spectra of the enzyme’s two metal-binding centers. Furthermore, a variant in which the catalytic Glu162 was deleted revealed the binding mode of oxalate, the first substrate-bound structure of OxDc. OxDc is a member of the cupin superfamily, which comprises a wide variety of proteins and enzymes with great sequence and functional diversity. A bioinformatics analysis of the superfamily was performed to analyze how sequence variation determines function and metal utilization. Chapters 3 and 4 discuss the expansion of lanthanide-binding tags (LBTs) to in cellulo studies. Lanthanide-binding tags are short sequences of amino acids that have high affinity and selectivity for lanthanide ions. An EGF-LBT construct used to quantify EGF receptors on the surface of A431 and HeLa cells. The results from the LBT quantification are consistent with previous studies of EGFR receptors in these cell types, validating the use of this method for future studies. The potential of using LBTs for X-ray fluorescence microscopy (XFM) was also investigated. LBT-labeled constructs were utilized to investigate if membrane bound as well as cytosolic LBT-containing proteins could be visualized and localized to their cell compartments via XFM; both membrane-localized and cytosolic proteins were successfully visualized. With the high resolution (< 150 Å) obtainable with new synchrotron beamline configurations LBTs could be used to study nanoscale biological structures in their near-native state.

Seventeen novel osmium cymene complexes with O,O′- and P,P′-chelating ligands as well as N- and P-monodentate ligands are reported. The osmium cymene complexes were synthesised and characterised by spectroscopic techniques (NMR, IR and Raman), elemental analysis, thermal analysis, conductivity studies and X-ray crystallography. The molecular structures of complexes 1(b), 2, 4, 6, 7(a)-(d) and 11 in this study are reported. The cymene rings of these complexes show different conformations due to loss of planarity influenced by the ancillary ligands as a result of ML back bonding. Osmium cymene complexes of the type [Os(η6-p-cymene)BrL2]+ (where L2 = chelating P,P′ ligand) and binuclear [{Os(η6-p-cymene)Br2}2 L2] (where L2 = bridging P,P′ ligand) were evaluated for anticancer activity against renal, melanoma, breast and HeLa cancer cells. The chelated-diphosphine osmium cymene complexes exhibited significant anticancer activities relative to the bridged-diphosphine osmium analogues. A series of O,O′-chelated osmium complexes exhibited moderate and poor anticancer activities. / Chemistry / M. Sc. (Chemistry)

Submitted by Natália Cecília Sartarelli (natalia_sartarelli@yahoo.com.br) on 2018-09-04T19:59:14Z No. of bitstreams: 1 Defesa Mestrado Natália C. Sartarelli - PPG Alimentos e Nutrição.pdf: 1871672 bytes, checksum: 8f9bb6f688029216469fbd2871954f16 (MD5) / Approved for entry into archive by Maria Irani Coito null (irani@fcfar.unesp.br) on 2018-09-04T22:53:10Z (GMT) No. of bitstreams: 1 sartarelli_nc_me_arafcf_par.pdf: 704578 bytes, checksum: ff79c882ecba32f7207c61c8873bc82f (MD5) / Made available in DSpace on 2018-09-04T22:53:11Z (GMT). No. of bitstreams: 1 sartarelli_nc_me_arafcf_par.pdf: 704578 bytes, checksum: ff79c882ecba32f7207c61c8873bc82f (MD5) Previous issue date: 2018-07-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Objetivos: Analisar quali e quantitativamente algumas hortaliças e frutos, quanto ao teor de ácido oxálico e avaliar o comportamento químico do ácido oxálico frente a agentes indutores e inibidores de cristalização in vitro. Métodos: A análise qualitativa morfológica de cristais de oxalato de cálcio foi feita sob microscopia ótica de luz polarizada e, quantitativamente foram determinados por método espectrofotométrico, os teores de ácido oxálico após extração com água e ácido clorídrico. Foram realizados também ensaios de indução de cristalização com cloreto de cálcio e inibição com sulfato de magnésio e citrato de sódio, respectivamente. Resultados: Foram identificados cristais de oxalato de cálcio do tipo drusas na alface; ráfides no cará e kiwi e, na rúcula e laranja não foi possível identificar o tipo morfológico do cristal presente. No estudo quantitativo observou-se diferença significativa entre as médias obtidas nas extrações aquosa e ácida somente para o cará, sendo superior na extração ácida. Observou-se ainda significância somente para a couve no ensaio quantitativo de cristalização; o acréscimo de sulfato de magnésio como agente inibidor da cristalização não foi significativo para todas as amostras avaliadas no estudo, no entanto, com o acréscimo de citrato de sódio houve aumento do conteúdo de ácido oxálico para o cará, inhame, laranja e kiwi. No estudo qualitativo dos ensaios de cristalização com cloreto de cálcio em microscopia ótica de luz polarizada observou-se presença de arranjos cristalinos; no ensaio com sulfato de magnésio observou-se presença de cristais poliédricos no kiwi, couve e laranja e, com o acréscimo de citrato de sódio observou-se presença de cristais menores somente em alface, cará, couve e inhame. Conclusão: Neste contexto, os teores de oxalato nas hortaliças e frutos estudados apresentam variações próprias conforme a matriz constitucional e, podem ser modificados com o acréscimo de cálcio e citrato. / Objectives: Analyze qualitatively and quantitatively some vegetables and fruits, regarding in the content of oxalic acid and evaluate the chemical behavior of the oxalic acid against inducers and inhibitors agents of the in vitro crystallization. Methods: The qualitative morphological analysis of calcium oxalate crystals was done under optical microscopy of polarized light and, quantitatively, the values of oxalic acid after extraction with water and hydrochloric acid were determined by spectrophotometric method. Tests inducting the crystallization with calcium chloride and inhibitioning with magnesium sulphate and sodium citrate, respectively, were also performed. Results: Druses calcium oxalate crystals were identified in lettuce; raphides in yam and kiwifruit; and in the arugula and orange it was not possible to identify the morphological type of the present crystal. In the quantitative study a significant difference was observed between the averages obtained in the aqueous and acid extractions only for the yam, being superior in the acid extraction. It was also observed a significance only for the wild cabbage in quantitative crystallization test. The addition of magnesium sulphate as a crystallization inhibitor was not significant for all the samples evaluated in the study. However, with the addition of sodium citrate there was an increase in the content of oxalic acid for yam, taro, orange and kiwifruit. Crystalline arrangements were observed in the qualitative study of crystallization tests with calcium chloride under optical microscopy of polarized light; in the test with magnesium sulphate it was noticed the presence of polyhedral crystals in kiwifruit, wild cabbage and orange and, with the addition of sodium citrate, small crystals were present only in lettuce, taro, wild cabbage and yam. Conclusion: In this context, oxalate contents in the vegetables and fruits that were studied have their own variations according to the constitutional matrix and, the oxalate content can be modified with the addition of calcium and citrate.

Foi sintetizada e caracterizada a spiro-ciclopentil-1,2-dioxetanona, um derivado de 1,2-dioxetanona inédito, de forma a se contribuir com informações acerca da quimiluminescência de peróxidos orgânicos. Estudos mecanísticos da decomposição quimiluminescente de 1,2-dioxetanonas são escassos, principalmente quando comparados à enorme quantidade de resultados existentes sobre a formação de estados excitados na decomposição de 1,2-dioxetanos. A spiro-ciclopentil-1,2-dioxetanona foi preparada pela ciclização do 1-carbóxi-1- hidroperóxiciclopentano com N,N-diciclohexilcarbodiimida, com rendimento de 1,2%, e caracterizada por RMN de 1H e 13C a baixa temperatura e pelo comportamento cromatográfico da solução peroxídica. Evidências para a ocorrência do mecanismo de Luminescência Iniciada Quimicamente por Troca de Elétron (CIEEL) na formação de estados excitados, na sua variante intermolecular, foram obtidas por estudos cinéticos da decomposição quimiluminescente dessa 1,2-dioxetanona por diferentes ativadores (ACTs). Entretanto, a decomposição desse peróxido ocorre com rendimentos de formação de estados excitados singlete baixos (&#934;S&#8776; 10-4 E mol-1), indicando que essa 1,2-dioxetanona também possui baixa eficiência de formação de estados excitados, conforme constatado recentemente para outros derivados. Foram encontradas evidências para a ocorrência de uma transferência de elétron na etapa limitante de velocidade, onde o ACT é formado no estado excitado, com um coeficiente de transferência de elétron de &#945; = 0,19. Ainda, foi observada uma correlação entre a energia livre liberada para a formação de estados excitados e os rendimentos quânticos, nos moldes do mecanismo CIEEL. De acordo com os resultados obtidos nesse trabalho e em trabalhos anteriores, postula-se que o tamanho do substituinte alquílico no anel da 1,2-dioxetanona causa um efeito drástico na eficiência da decomposição catalisada do peróxido na seqüência CIEEL, diminuindo o valor da constante de equilíbrio para a formação inicial do complexo de transferência de carga Em uma segunda parte do trabalho, foi averiguado o mecanismo da reação peróxi-oxalato em meios aquosos, uma vez que a maioria dos trabalhos sobre esta transformação nestes meios possui ênfase na aplicação analítica. Foi observado que as reações dos oxalatos de bis(2,4,6-triclorofenila) (TCPO), moderadamente reativo, e bis(2,4-dinitrofenila) (DNPO), altamente reativo, com H2O2 e catálise por imidazol, ocorrem pelo mesmo mecanismo, em 1,2-dimetoxietano e em misturas aquosas desse solvente. Para TCPO, observou-se que há a formação de um intermediário de catálise nucleofílica, previamente ao ataque nucleofílico do H2O2. Para DNPO, há uma adição nucleofílica direta do H2O2 ao éster, com e sem catálise básica por imidazol. Em meios aquosos, a hidrólise do éster oxálico ocorre paralelamente à peridrólise, que leva à emissão de luz. Entretanto, as constantes de velocidade para a peridrólise do éster são significativamente maiores do que as para a sua hidrólise. Observou-se que a reação de TCPO com H2O2 em meios orgânico e aquoso, catalisada por 2,6-lutidina (2,6-dimetilpiridina), ocorre com essa base agindo como um catalisador não-nucleofílico. Por último, estudou-se a reação de TCPO com H2O2 em tampão carbonato de potássio, um meio essencialmente aquoso, onde a espécie reativa é a base conjugada do H2O2; entretanto, a constante de velocidade da peridrólise se mostrou similar à de hidrólise do éster oxálico. Nessa última parte do trabalho, foi demonstrado que a reação peróxi-oxalato também pode ser conduzida em meios aquosos. / Spiro-cyclopentyl-1,2-dioxetanone, a new 1,2-dioxetanone derivate, was synthesized and characterized, in order to contribute to the present mechanistic knowledge on organic peroxide chemiluminescence. Mechanistic studies on the chemiluminescent 1,2-dioxetanone decomposition are highly limited, especially when compared to the huge amount of data available for 1,2-dioxetanes. The spiro-cyclopentyl-1,2-dioxetanone was prepared by 1-carboxy-1-hydroperoxycyclopentane cyclization with N,N-dicyclohexylcarbodiimide, in a 1.2% yield and characterized by low temperature 1H and 13C NMR and the chromatographic behavior of the peroxide solution. Evidence for the occurrence of the Chemically Initiated Electron Exchange Luminescence (CIEEL) mechanism for excited states formation, in its intermolecular version, was obtained from kinetic studies of the chemiluminescent decomposition of this 1,2-dioxetanone with different activators (ACTs). However, the decomposition of this peroxide occurs with low yields of singlet excited state formation (&#934;S&#8776; 10-4 E mol-1), showing that also this 1,2-dioxetanone possesses low excitation efficiency, as recently found for other derivatives. Evidence was found for the occurrence of an electron transfer in the rate limiting step, where the ACT is formed in its electronically excited state, with an electron transfer coefficient &#945;= 0.19. Moreover, a correlation between the free energy released upon excited states formation and the quantum yields is observed, in agreement with the CIEEL mechanism. The results obtained in the present work together with previous data, allow to postulate that the size of the alkyl substituent on the 1,2-dioxetanone ring plays a crucial role for the efficiency of the catalyzed peroxide decomposition in the CIEEL sequence, by lowering the equilibrium constant for initial charge transfer complex formation. In a second part of this work, the mechanism of the peroxyoxalate reaction in aqueous media was studied, due to the fact that most of recent work on this system is mainly concerned only to analytical application aspects. The reaction of the moderately reactive bis(2,4,6-trichlorophenyl) (TCPO) and the highly reactive bis(2,4- dinitrophenyl) oxalate (DNPO) with H2O2 and imidazol catalysis, showed to occur by the same mechanism, in 1,2-dimethoxyethane as well as in its aqueous mixtures. For TCPO, the formation of an intermediate due to nucleophilic catalysis by imidazole was observed, preceding the H2O2 nucleophilic attack. For DNPO, direct nucleophilic addition of H2O2 to the ester occurs, with and without imidazole catalysis. In aqueous media, oxalic ester hydrolysis also occurs concomitantly to its perhydrolysis, which leads to light emission. However, the rate constants for perhydrolysis are significantly higher than the hydrolysis rate constants. For the reaction of TCPO with H2O2 in organic and aqueous medium, catalyzed by 2,6-lutidine (2,6-dimethylpyridine), it was shown that this base acts as a nonnucleophilic catalyst. Finally, the reaction of TCPO with H2O2 in potassium carbonate buffer, an essentially aqueous media, was studied, where the reactive species is the H2O2 conjugate base; however, the oxalic ester perhydrolysis rate constant proofed to be similar to its hydrolysis rate constant. In this last part it is also shown that the peroxyoxalate reaction can be carried out in aqueous media.

This report describes a new group of anaerobic bacteria that degrade oxalic acid. The new genus and species, Oxalobacter formigenes, are inhabitants of the rumen and also of the large bowel of man and other animals where their actions in destruction of oxalic acid may be of considerable importance to the host. Isolates from the rumen of a sheep, the cecum of a pig, and from human feces were all similar Gram-negative, obligately anaerobic rods, but differences between isolates in cellular fatty acid composition and in serologic reaction were noted. Measurements made with type strain OxB indicated that 1 mol of protons was consumed per mol of oxalate degraded to produce approximately 1 mol of CO2 and 0.9 mol of formate. Substances that replaced oxalate as a growth substrate were not found.