Direct methanol fuel cells (DMFCs) are considered a clean source of electrical power for future energy demand, creating a potential to reduce our dependency on fossil fuels. Despite their advantages, including high energy density, efficiency and easy handling and distribution of fuel, the commercialization of DMFCs has suffered from some drawbacks, including methanol crossover and contamination of the system. Metal cation contaminants (such as Ni, Co, etc) introduced through the degradation of fuel cell components (bipolar plate and electro-catalyst layer) can significantly affect the Nafion-membrane properties and overall fuel cell performance. In the current study, a systematic approach is taken to characterize and identify the mechanism of the effect of metal solution contaminants on the activities of electro-catalysts of DMFCs. Cyclic voltammetry and rotating disk electrode (RDE) techniques were utilized in order to characterize the effect of various concentrations (i.e., 2x10-x M (x=1-7)) of six metal solution contaminants (i.e., Co, Ni and Zn with sulfate and nitrate as counter-anions) on the voltammetric properties and electro-catalytic activity of polycrystalline Pt during methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). The results showed a decrease in the MOR and ORR activities of Pt as the concentration of metal solution increased. The effect of counter-anion on the Pt activity was further investigated. The results showed that a combined effect of counter-anions and metal cations may be responsible for the decrease in the electro-catalytic activity of Pt. The effect of metal solution contaminants on the Nafion-ionomer of anode electro-catalysts was investigated using Nafion-coated Pt electrode. Voltammetric properties and MOR activities of Nafion-coated and bare Pt electrodes in the presence of Ni solution contaminants were characterized using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The overall results showed a significant negative effect of Ni solution contaminants on the electro-catalytic activity of bare Pt electrode as compared to the Nafion-coated Pt electrode. Based on the results, it appears that Nafion-ionomer film may interact with metal cations (through its sulfonate groups) and repel them away from the Pt active sites, partially inhibiting the negative effect of metal cations on the Pt activity of Nafion-coated Pt electrode. The effect of metal solution contaminants on the carbon-supported platinum nanoparticle (Pt/C) with various Nafion-ionomer distributions and contents (i.e., Nafion-incorporated Pt/C and Nafion-coated Pt/C electrodes) was further investigated. Cyclic voltammetry and EIS techniques were employed to characterize the effect of Ni solution contaminants on the voltammetric properties and MOR activities of Nafion-incorporated and Nafion-coated Pt/C electrodes. The overall results showed a stronger negative effect of Ni solution contaminants on the electro-catalytic activity of Nafion-incorporated Pt/C electrodes as compared to the Nafion-coated Pt/C electrodes. This further confirms previous observations showing the sulfonate groups of Nafion-ionomer film may attract the Ni metal cations, localize them away from the Pt active sites, and subsequently suppress the negative effect of cations on the activity of Nafion-coated Pt/C electrodes.

Ho, Yuk Ting. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references. / Abstracts in English and Chinese. / Acknowledgement --- p.i / Abstract --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Composite Materials --- p.1 / Chapter 1.2 --- General Properties of Composite Materials --- p.2 / Chapter 1.3 --- Fabrication of Composite Materials --- p.3 / Chapter 1.3.1 --- Liquid State Sintering --- p.4 / Chapter 1.3.2 --- Casting --- p.6 / Chapter 1.3.3 --- Other Fabrication Techniques --- p.7 / Chapter 1.4 --- Phase Transformation --- p.8 / Chapter 1.5 --- Nucleation and Growth --- p.10 / Chapter 1.5.1 --- Homogeneous nucleation --- p.10 / Chapter 1.5.2 --- Heterogeneous nucleation --- p.10 / Chapter 1.5.3 --- Growth --- p.11 / Chapter 1.6 --- Phase Separation by Spinodal Decomposition --- p.11 / Chapter 1.6.1 --- The Initiation of Spinodal Decomposition --- p.12 / Chapter 1.6.2 --- Dynamics of Spinodal Decomposition --- p.12 / Chapter 1.6.3 --- Difference between Coherent Spinodal and Nucleation and Growth --- p.17 / Chapter 1.7 --- Methods in Obtaining Large Under-cooling --- p.19 / References --- p.20 / Figures --- p.23 / Chapter Chapter 2 --- Experiment --- p.29 / Chapter 2.1 --- Introduction --- p.29 / Chapter 2.2 --- Preparation of Fused Silica Tubes --- p.29 / Chapter 2.3 --- Sample Preparation --- p.30 / Chapter 2.3.1 --- Alloying --- p.30 / Chapter 2.3.2 --- Fluxing --- p.30 / Chapter 2.3.3 --- Under-cooling --- p.31 / Chapter 2.4 --- Microstructure Analysis --- p.32 / Chapter 2.4.1 --- Sample Surface Analysis --- p.32 / Chapter 2.4.2 --- Scanning Electron Microscopy (SEM) --- p.32 / Chapter 2.5 --- Transmission Electron Microscopy (TEM) --- p.32 / Chapter 2.5.1 --- Specimen Requirement --- p.33 / Chapter 2.5.2 --- "Cutting, Grinding, Polishing and Pouching" --- p.33 / Chapter 2.5.3 --- Dimpling --- p.34 / Chapter 2.5.4 --- Ion Milling --- p.34 / Chapter 2.5.5 --- Microstructure Characterization by TEM --- p.35 / Chapter 2.6 --- Mechanical Properties --- p.37 / Chapter 2.6.1 --- Hardness Testing --- p.37 / Chapter 2.6.2 --- Compression Testing --- p.37 / Chapter 2.7 --- Characterizations of Untreated Samples --- p.38 / References --- p.39 / Figures --- p.40 / Chapter Chapter 3 --- Formation and Properties of Co-Si-B Metal Matrix Composites --- p.44 / Abstract --- p.44 / Introduction --- p.45 / Experimental --- p.46 / Results --- p.47 / Chapter A. --- Microstructures --- p.48 / Eutectic Co75Si15B10 --- p.48 / Network Co75Si15B10 --- p.48 / Chapter B. --- Mechanical Behavior --- p.50 / Eutectic Co75Si15B10 --- p.50 / Network CO75Si15B10 --- p.51 / Discussions --- p.53 / Conclusion --- p.53 / Acknowledgement --- p.54 / References --- p.55 / Figures --- p.56 / Chapter Chapter 4 --- On the Network Morphology of Co75Si15B10 Alloys --- p.68 / Abstract --- p.68 / Introduction --- p.69 / Experimental --- p.69 / Results --- p.69 / Discussions --- p.74 / Acknowledgement --- p.77 / References --- p.78 / Figures --- p.79 / Chapter Chapter 5 --- Conclusion --- p.100

Com o objetivo de avaliar a maneira como a aplicação foliar no estádio fenológico V5, do herbicida pós-emergente Lactofen em mistura com os micronutrientes Co e Mo, pode interferir com o crescimento e a produtividade da cultura da soja, cv. Conquista, o presente trabalho de pesquisa foi conduzido em duas áreas experimentais da Escola Superior de Agricultura \"Luiz de Queiroz\" (USP/ESALQ), em Piracicaba-SP: uma na Fazenda Areão, durante os anos agrícolas de 2003/04, 2004/05 e 2005/06 em solo LATOSSOLO VERMELHO Distrófico argiloso e outra na Estação Experimental de Anhembi, durante os anos agrícolas 2003/04 e 2005/06 em solo LATOSSOLO AMARELO Distrófico típico. Delineado experimentalmente sob blocos ao acaso com quatro repetições, os onze tratamentos constaram de diferentes formas de aplicação e interações entre os micronutrientes Co e Mo e o herbicida pós-emergente Lactofen: T1 = controle; T2 = tratamento de sementes com Co e Mo; T3 = tratamento de sementes com Co e Mo + aplicação de herbicida em V5; T4 = aplicação foliar de Co e Mo em V5; T5 = aplicação foliar de Co e Mo + herbicida em V5; T6 = aplicação de herbicida em V5 + foliar de Co e Mo 3 a 5 dias após; T7 = aplicação foliar de Co e Mo em V5 + aplicação de herbicida 3 a 5 dias após; T8 = aplicação foliar de Co em V5; T9 = aplicação foliar de Co + herbicida em V5; T10 = aplicação foliar de Mo em V5; T11 = aplicação foliar de Mo + herbicida em V5; Os parâmetros avaliados foram: pH das soluções de Lactofen e de micronutrientes; avaliação da fitotoxicidade causada pelo herbicida Lactofen; análise do estado nutricional das plantas em N, Co e Mo; altura final de planta; altura de inserção da primeira vagem; número de ramificações; número de vagens e de grãos por planta; grau de acamamento; peso de 1000 grãos e produtividade agrícola. Concluiu-se que: a) fornecimento de cobalto e molibdênio para a soja, cultivar Conquista, via tratamento de sementes ou via foliar, a partir de sais desses micronutrientes, pode diminuir o peso de mil grãos e a produtividade agrícola da cultura; b) a aplicação foliar do herbicida Lactofen no estádio fenológico V5 da soja, cultivar Conquista, pode interferir negativamente com o crescimento vegetativo, resultando na redução da altura final de planta, do peso de mil grãos e da produtividade agrícola da cultura; c) a aplicação foliar do herbicida Lactofen no estádio fenológico V5 da cultura da soja causa fitotoxicidade às folhas, em grau variável de leve a médio. / The purpose of this work was to evaluate how foliar applications of the post-emergence herbicide Lactofen mixed with the micronutrients Co and Mo at V5 phenological stage influence the growth and productivity of soybean, cv. Conquista. The study was conducted in two experimental areas of Escola Superior de Agricultura \"Luiz de Queiroz\" (USP/ESALQ), Piracicaba-SP. One of them was located in the Areão Farm, in a clay Oxisol, during the crop years 2003/04, 2204/05 and 2005/06. The other was located in the Anhembi Experimental Station, in an Oxisol, during the crop years of 2003/04 and 2005/06. The eleven treatments tested involved different application procedures and interactions between the micronutrients Co and Mo and the post-emergence herbicide Lactofen in a randomized block design, with four replicates. Treatments were T1 = control; T2 = seeds treated with Co and Mo; T3 = seeds treated with Co and Mo + herbicide application at V5 stage; T4 = foliar-applied Co and Mo at V5 stage; T5 = foliar-applied Co and Mo + herbicide application at V5 stage; T6 = herbicide application at V5 stage + foliar-applied Co and Mo 3 to 5 days after herbicide application; T7 = foliar-applied Co and Mo at V5 stage + herbicide application 3 to 5 days after micronutrients application; T8 = foliar-applied Co at V5 stage; T9 = foliar-applied Co + herbicide application at V5 stage; T10 = foliar-applied Mo at V5 stage; T11 = foliar-applied Mo + herbicide application at V5 stage. The parameters evaluated were: pH of Lactofen and micronutrient solutions; phytotoxicity caused by Lactofen; analysis of plant nutritional state regarding N, Co and Mo; final plant height; insertion height of the first pod; number of branches per plant; number of pods and grains per plant; lodging level; mass of 1,000 grains and yield. It was concluded that: a) the application of Co and Mo salts to soybean, cv. Conquista, whether foliar applied or used in seed treatment, may reduce the mass of 1,000 grains and crop productivity; b) the foliar application of Lactofen to soybean, cv. Conquista, at V5 phenological stage may affect the vegetative growth negatively, reducing the plant final height, the mass of 1,000 grains and the yield; c) the foliar application of Lactofen to soybean at V5 V5 phenological stage leads to leaf phytotoxicity at mild to moderate levels.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the academic requirements for the degree of Doctor of Philosophy. Johannesburg, 2014. / Unable to load abstract.

Neste trabalho foram avaliadas as atividades de catalisadores do tipo perovskita LaNi1-xCoxO3 frente à reação de reforma a vapor de etanol. Devido à baixa área superficial, característica de óxidos do tipo perovskita, esses foram suportados em SiO2, Al2O3 e ZrO2, a fim de verificar o efeito do suporte na atividade catalítica.<br /> Os catalisadores foram preparados pelo método da co-precipitação e caracterizados por espectrometria de emissão atômica por plasma induzido, difração de raios X pelo método do pó, adsorção de nitrogênio pelo método B.E.T, redução a temperatura programada e espectroscopia de absorção de raios X.<br /> Para estudar o processo de redução e a possibilidade de oxidação durante a reação catalítica, foram realizados estudos in situ da reação de reforma a vapor, através da espectroscopia de absorção de raios X. Estes dados foram comparados com os resultados de aplicação das técnicas de RTP e DRX às amostras parcial e totalmente reduzidas e foi proposto um mecanismo de redução do óxido do tipo perovskita durante o processo de ativação do catalisador.<br /> Todos os catalisadores mostraram-se ativos nas reações de reforma a vapor de etanol e a seletividade dos produtos foi dependente do tipo do catalisador avaliado. De acordo com os resultados obtidos, destaca-se o catalisador não suportado LaNiO3, com conversão de etanol de 99% e seletividade para H2, CO e CO2 de 4,8; 1,1 e 1,3, respectivamente. Além disso, o ensaio com dois catalisadores simultâneos (LaNiO3 + LaCoO3) foi o que apresentou melhor estabilidade na reação, com 100% de conversão de etanol e seletividade semelhante à obtida pelo catalisador LaNiO3. / In this work, the catalytic activity of perovskite oxides, LaNi1-xCoxO3, was evaluated in the ethanol steam reforming. Due to the low surface area, characteristic of perovskite oxides, these catalysts were supported on SiO2, AI2O3 and ZrO2 and the effect of the support was evaluated. The catalysts were prepared by the co-precipitation method and characterized by Atomic Induced Plasma Spectroscopy, X-Ray Powder Diffraction (XRD), Nitrogen adsorption by B.E.T. method, Temperature Programmed Reduction (TPR) and X-ray Absorption Near Edge Structure (XANES).<br /> The catalytic process was accompanied by XANES in situ to verify changes in the oxidation state of the active phase during the activation process with H2 and also during the process of steam reforming of ethanol. By relation of these results with TPR and XRD, for samples partially and fully reduced, it was proposed a mechanism for the reduction of the perovskite oxides during the conditions of activation.<br /> All catalysts showed activity for the ethanol steam reforming with the selectivity dependent of the catalyst evaluated. Summarizing, the results showed that the unsupported catalyst LaNiO3 presented the better performance, with the ethanol conversion of 99% and selectivity for H2, CO and CO2 of 4.8; 1.1 and 1.3, respectively. Moreover, the test using two simultaneous catalysts (LaNiO3 + LaCoO3), showed better stability in the reaction, presenting ethanol conversion of 100% and selectivity to H2, CO and CO2 similar to the LaNiO3 catalyst.

Density Functional Theory (DFT) is a powerful tool for treating large organometallic structures efficiently and accurately. DFT calculations on the Hg-catalyzed oxidation of methane to methyl bisulfate in sulfuric acid suggest the lowest energy pathway involves a closed-shell electrophilic C–H activation mechanism coupled with metal alkyl reductive functionalization and oxidation by SO3. Comparison to Tl, Zn, and Cd suggests that Hg is unique in its ability to catalyze this set of reaction steps. Comparison to K2S2O8 highlights the selectivity of this C–H activation reaction as opposed to radical conditions. In contrast, DFT calculations indicate that CoIII(TFA)3 oxidizes methane through a radical TFA ligand decarboxylation pathway. A similar decarboxylation pathway is identified for MnIII(TFA)3, but the low spin ground state of TlIII(TFA)3 favors electrophilic C–H activation over this decarboxylation pathway. DFT calculations indicate that Cp(PPh2Me)Co=CF2 undergoes [2 + 2] cycloaddition with TFE by a unique open-shell singlet diradical mechanism. The significant stability of the perfluorometallacyclobutane reveals why catalytic metathesis with TFE is difficult.

Thesis ((MSc. (Physics)) -- University of Limpopo, 2018 / The mechano-chemical technique was employed to synthesise the undoped, cobalt and indium single and double doped ZnO nanoparticles powder samples. The x-ray diffraction (XRD), scanning electron microscopy (SEM), raman spectroscopy (RS), ultraviolet-visible spectroscopy (UV-vis), and photoluminescence (PL) spectroscopy were employed to characterise the prepared samples. The XRD and energy dispersive spectroscopy (EDS) results confirmed that the prepared samples were of hexagonal wurzite form. In addition, it was found that the diffraction pattern for In-ZnO nanoparticles display an additional peak which was associated with In3+ dopant. The peak suggest that In3+ ions prefer the interstitial site in the hexagonal ZnO structure. Doping the ZnO nanoparticles with Co and In did not significantly affect the lattice parameters but the average grain sizes of the nanoparticles were found to be reduced. The morphology of the samples revealed by the SEM images appear to be more spherical. The Raman modes obtained from the excitations wavelength of 514.532 nm further indicated that the prepared samples were of hexagonal ZnO structures. The energy band gap of the prepared samples were calculated from the UV-vis data which showed that the doped ZnO nanoparticles had smaller energy band gap compared to the undoped ZnO nanoparticles. The excitation wavelength of 350 nm were used in the PL study where various defects related emissions were observed for the doped and undoped ZnO nanoparticles. The kenosistec station equipment was used to investigate the prepared samples for gas sensing application. Ammonia (NH3), methane (CH4) and hydrogen sulphide (H2S) gases were probed. In all the response curves observed, the undoped and double doped ZnO nanoparticles are being favoured at a temperature range 200 – 350oC. In addition, the double doped ZnO nanoparticles was found to be more sensitive to CH4 at low temperatures and low v concentrations. / National Research Foundation (NRF) and Council for Scientific and Industrial Research (CSIR)

Ce travail de thèse est consacré au développement de nouvelles méthodologies en catalyse mettant en jeu des complexes métalliques à base de métaux non nobles, en l’occurrence le cobalt et le niobium. Ces deux métaux ont été utilisés pour catalyser des réactions d’hydrofonctionnalisation de liaisons multiples carbone‒carbone. L’objectif était de proposer des systèmes catalytiques compétitifs à base de métaux non précieux et de promouvoir leur utilisation par rapport à d’autres métaux peu abondants et onéreux. Un complexe de cobalt bien défini, HCo(PMe3)4, a été employé pour catalyser des réactions d’hydroboration régio- et stéréosélectives d’alcynes internes, ainsi que des réactions de diboration d’alcynes. D’autre part, un système catalytique au niobium(V) cationique a été mis au point et utilisé pour diverses réactions d’hydrofonctionnalisation intramoléculaires, permettant la synthèse d’une large famille d’hétérocycles. De manière à mettre encore davantage en lumière ce métal et ces bienfaits, des travaux ont été réalisés en catalyse énantiosélective. Un système catalytique chiral de niobium(V) a été utilisé pour l’hydroalkoxylation d’alcènes énantiosélective. Des résultats encourageants ont été obtenus même si ce système doit encore être optimisé et testé en présence de différents hydroxyalcènes. / This PhD work has focused on the development of new methodologies in catalysis based on non-noble metals: cobalt and niobium. These two metals have been used to catalyze hydrofunctionalization reactions of carbon‒carbon multiple bonds. The aim of those projects was to propose competitive catalytic systems based on non-precious metals and to promote their use compared to other rare and expensive metals. To this end, we successfully demonstrated that a well-defined cobalt complexe HCo(PMe3)4 is an efficient catalyst for regio- and stereoselective hydroboration reactions of internal alkynes, as well as diboration reactions. Also, a new catalytic system based on cationic niobium(V) has been developed and used to catalyze intramolecular hydrofunctionalization reactions leading to the synthesis of a large family of heterocycles. In order to reveal even more the potential of niobium in catalysis, we aimed to propose a chiral system able to catalyze enantioselective hydroalkoxylation of alkenes. Despite the promising results, some more efforts on the optimization of this system still need to be done.

The design and development of nanoparticles is of great interest in the current energy and electronic industry. However, based on the current materials available the production cost can be high with insignificant magnetic and mechanical properties. Specifically, rare-earth magnetic materials composed of neodymium and samarium are known for their high magnetic performance, however, due to the cost of development there is a need to develop a versatile and cost effective material. Alternatively, cobalt carbide nanomaterials have shown to be a promising alternative for rare-earth free magnets as they exhibit comparable properties as hexaferrite magnetic materials. The primary goal of this dissertation focuses on the development of nanoparticles for permeant magnetic, and magnetic refrigeration applications. The first part of this work focuses on the synthesis of cobalt carbide (CoxC, x=2,3) nanoparticles using a novel polyol synthesis method by introducing a small amount of Ru, Cu, or Au as nucleating agent. It was found that the morphology and magnetic properties of the as-synthesized CoxC nanoparticles change as a result of directional growth of nanoparticles using nucleating agents. Needle-like particle morphology ranges from 20-50 nm in width and as long as 1 µm in length were synthesized using Ru as nucleating agent. These particles exhibit magnetization saturation of 33.5 emu/g with a coercivity of 2870 Oe and a maximum energy product 1.92 MGOe (BHmax) observed. Particle morphology is a critical aspect in the development of magnetic nanoparticles as anisotropic particles have shown increased coercivity and magnetic properties. These CoxC nanomaterials have a higher maximum energy product compared to previous work providing further insight into the development of non-rare earth magnetic material. The second part of this dissertation work focuses on the sol-gel synthesis of perovskite LaCaMnO3 (LCMO) nanomaterials. In this process, various chain lengths of polyethylene glycol (PEG) was added into a solution consisting of La, Ca, and Mn salts. The solution was left for the gelation process, and high temperature sintering to obtain the final product. By varying the polymer chain of the PEG, the size of the as synthesized LaCaMnO3 nanomaterials were altered. The as-synthesized LCMO nanomaterials have shown a maximum change in magnetic entropy (-ΔSM) was found to be 19.3 Jkg-1K-1 at 278 K for a field change of 0-3 T and 8.7 Jkg-1K-1 for a field change of 0-1 T. This is a significant improvement in comparison to current literature of the material suggesting that this is a promising alternative to Gd materials that is prone to oxidation. With additional development, LCMO or related maganites could lead to application in commercial technologies.

Proteoglycans containing Heparan Sulfate (HS), a sulfated glycosaminoglycan (GAG), play a major role in the cell signaling process, interacting with many different proteins. HS is over expressed on the surface of many cancer cells. Enzymatic cleavage of HS-GAGs by heparanase causes release of angiogenic growth factors leading to tumor cell migration. Heparanase is also over-expressed in tumors with significant correlation between metastatic potential and heparanase activity. Proteoglycans and their associated enzymes are thus significant drug targets of high biological relevance. A functional consequence of strong PPC-HS binding has been shown in proof-of-concept studies confirming inhibition of the model pentasaccharide, Fondaparinux, by bacterial Heparinase. Such metalloshielding by PPCs may also protect HS from enzymatic cleavage by the mammalian heparanase; preventing growth factors from binding to HS and/or preventing release of bound growth factors and thus inhibiting the metastatic response in the cancer cells. HS-GAGs are also receptors for cellular accumulation of cationic Polynuclear Platinum Complexes (PPCs) through high-affinity binding to the highly anionic HS. PPCs competitively inhibit uptake of TAMRA-R9, a fluorescent nona-arginine derivative, in CHO cells. The previously reported series of Pt(II) complexes were investigated as DNA binders, initiating the apoptotic cascade. The result of PPC-DNA binding produces long range inter and intra-strand cross-links, that produce structural and conformational changes. Hydrogen bonding between phosphate oxygens and square planar Pt(II) nitrogen results in bidentate complexes by either backbone tracking or groove spanning of DNA. This complex forms a clamp like structure, called a phosphate clamp, similar to that of the arginine fork. Understanding this clamp allows us to investigate the structurally similar sulfate binding between metal complexes and target HSPG. HSPGs may allow significant research into both a novel cellular internalization of principal metals and “metalloshielding” of heparin by these compounds. Previous studies have shown that a wide range of metal ions have high affinity to heparin. The trend of metal/heparin affinity is believed to be dependent on parameters consisting of the metal’s overall size, spatial orientation of the ligands attached to each metal, the net charge and oxidation state of these metals, and number of binding sites. Studies have shown relative affinities of sulfate and carboxylate groups for the metal ions. These metal cations play an important role in the affinity, specificity, and stability of many protein/heparin interactions. The study of simple coordination compounds, like Pt, Mn, V, Ru and Co, will allow preliminary results which will extend into the PPCs mode of binding. This thesis focuses on the concept of metalloglycomics and reviews the interactions of various metal complexes with heparin. The covalent and non-covalent interactions of metal complexes with heparin resulting in strong bonding are explained through spectroscopy and calorimetry. The cleavage inhibition of heparanase by metal complexes is also described. Sulfate cluster anchoring shields the sulfates from loss as seen in mass spectrometry. The study of metalloglycomics offers potential understanding into the relevance of metal-heparin interactions and possibilities into the development of new compounds as therapeutic agents.