Effects of methyl mercury at different dose regimes on eggshell formation and some biochemical characteristics of the eggshell gland mucosa of the domestic fowl

Eggshell formation and egg production in domestic fowl were studied following the administration of methyl mercury (two dose regimes: 5 mg daily for 6 consecutive days and 1 mg daily for 50 consecutive days). A daily oral dose of 5 mg of methyl mercury for 6 consecutive days induced significant eggshell thinning and deformation and inhibited egg production. Uptake of ⁴⁵Ca and synthesis of prostaglandins by a homogenate of eggshell gland mucosa from methyl-mercury-treated birds were significantly reduced, as was the calcium content of blood plasma. A daily oral dose of 1 mg of methyl mercury administered for 50 consecutive days also induced eggshell deformation and thinning and reduced egg production. This dose did not, however, have significant effects on the following: ⁴⁵Ca uptake and prostaglandin synthesis by a homogenate of the eggshell gland mucosa; ⁴⁵Ca uptake by a homogenate of duodenal mucosa; the Ca content of the blood plasma, shell gland mucosa or shell gland lumen; the HCO₃⁻ content of the shell gland lumen or the specific gravity of tibia. Methyl mercury added in vitro to a homogenate of eggshell gland mucosa significantly stimulated the synthesis of prostaglandins PGF_2α and PGE₂. Addition of mercury chloride to the same type of preparation stimulated the synthesis of PGF_2α at the expense of thromboxane (T × B₂) synthesis. Administration of 5 mg methyl mercury for 6 consecutive days seemed to reduce the availability of calcium for eggshell formation. This effect could have been due to a direct inhibitory effect of methyl mercury on calcium uptake from the gastrointestinal tract and/or to mobilization of medullary bone. The administration of 1 mg methyl mercury for 50 consecutive days probably induced the reproductive effects by another mechanism. The effects of methyl mercury on avian eggshell formation are quite different from the effects p,p′-DDE exerts on that process.     

Sulfhydryl Group Involvement in Plasmalemma Transport of HCO(3) and OH in Chara corallina

The effect of the sulfhydryl reagents (—SH) p-chloromercuribenzene-sulfonic acid (PCMBS), N-ethylmaleimide (NEM), and inorganic mercury on H¹⁴CO₃⁻ assimilation in Chara corallina is reported. Commercial grade PCMBS caused severe inhibition of H¹⁴CO₃⁻ assimilation. Results obtained using purified PCMBS (stock solution passed through a chelating resin) indicated that inhibition observed using unpurified PCMBS was due predominantly to the presence of inorganic mercury (as a contaminant). The inhibitory role of inorganic mercury was verified using HgCl₂. This chemical caused a dramatic inhibition of H¹⁴CO₃⁻ assimilation, while it had little effect on cellular ¹⁴CO₂ fixation. Reversal of the Hg²⁺ inhibition of H¹⁴CO₃⁻ assimilation (in presence of 1.0 millimolar dithioerythritol) was extremely slow, requiring 2 to 3 hours for the reestablishment of control rates. This slow recovery may reflect de novo synthesis of transport proteins.     

Characterization of crystalline structures in Opuntia ficus-indica

This research studies the crystalline compounds present in nopal (Opuntia ficus-indica) cladodes. The identification of the crystalline structures was performed using X-ray diffraction, scanning electron microscopy, mass spectrometry, and Fourier transform infrared spectroscopy. The crystalline structures identified were calcium carbonate (calcite) [CaCO₃], calcium-magnesium bicarbonate [CaMg(CO₃)₂], magnesium oxide [MgO], calcium oxalate monohydrate [Ca(C₂O₄)•(H₂O)], potassium peroxydiphosphate [K₄P₂O₈] and potassium chloride [KCl]. The SEM images indicate that calcite crystals grow to dipyramidal, octahedral-like, prismatic, and flower-like structures; meanwhile, calcium-magnesium bicarbonate structures show rhombohedral exfoliation and calcium oxalate monohydrate is present in a drusenoid morphology. These calcium carbonate compounds have a great importance for humans because their bioavailability. This is the first report about the identification and structural analysis of calcium carbonate and calcium-magnesium bicarbonate in nopal cladodes, as well as the presence of magnesium oxide, potassium peroxydiphosphate and potassium chloride in these plants. The significance of the study of the inorganic components of these cactus plants is related with the increasing interest in the potential use of Opuntia as a raw material of products for the food, pharmaceutical, and cosmetic industries.     

Mercury affects uterine myogenic activity even without producing any apparent toxicity in rats: Involvement of calcium-signaling cascades

BackgroundMercury is an established environmental toxicant reported to cause reproductive disorders in women, however, its direct action on myometrial activity is yet to be understood. Earlier we have reported the underlying mechanism of mercury-induced myometrial contractions following in vitro exposure; however, no such information on the effect of mercury on myometrial activity following in vivo exposure is available, therefore, the present study was undertaken.ObjectivePresent study was designed to evaluate the effect of mercury on myometrial activity following in vivo exposure of rats and unravel the possible underlying mechanism.MethodsFemale Wistar rats were orally exposed to mercury (5, 50 and 500 μg/L in drinking water) for 28 days to investigate the toxicodynamics of mercuric chloride (HgCl₂)-induced alterations in myometrial activity. Response of the isolated myometrial strips to different spasmogens was recorded using polyphysiograph. Blood and uterine calcium, mercury, iron and zinc levels were estimated by atomic absorption spectrophotometry. Blood biochemicals and serum hormonal profiles (estradiol, progesterone) were also determined.ResultsNo systemic toxicity of mercury was observed in any of the treatment groups (5, 50 and 500 μg/L) in terms of alterations in body weight, organ weights, blood biochemical parameters including hormonal profile. Interestingly, mercury at 5 μg/L concentration significantly increased the receptor-dependent (PGF_2α-induced) and receptor-independent (CaCl₂-induced and high K⁺-depolarizing solution-induced) myometrial contractions and it was coupled with corresponding increase in the uterine calcium levels. However, mercury at higher dose levels (50 and 500 μg/L) did not significantly alter the myometrial response.ConclusionOur results evidently suggest that mercury at low level (5 μg/L) produced detrimental effect on myometrial activity by altering calcium entry into the smooth muscle and/or the release of calcium from intracellular stores without causing any apparent systemic toxicity in rats.     

Towards a computational reconstruction of the electrodynamics of premature and full term human labour

We apply virtual tissue engineering to the full term human uterus with a view to reconstruction of the spatiotemporal patterns of electrical activity of the myometrium that control mechanical activity via intracellular calcium. The three-dimensional geometry of the gravid uterus has been reconstructed from segmented in vivo magnetic resonance imaging as well as ex vivo diffusion tensor magnetic resonance imaging to resolve fine scale tissue architecture. A late-pregnancy uterine smooth muscle cell model is constructed and bursting analysed using continuation algorithms. These cell models are incorporated into partial differential equation models for tissue synchronisation and propagation. The ultimate objective is to develop a quantitative and predictive understanding of the mechanisms that initiate and regulate labour.     

The Use of a Mercury Biosensor to Evaluate the Bioavailability of Mercury-Thiol Complexes and Mechanisms of Mercury Uptake in Bacteria

As mercury (Hg) biosensors are sensitive to only intracellular Hg, they are useful in the investigation of Hg uptake mechanisms and the effects of speciation on Hg bioavailability to microbes. In this study, bacterial biosensors were used to evaluate the roles that several transporters such as the glutathione, cystine/cysteine, and Mer transporters play in the uptake of Hg from Hg-thiol complexes by comparing uptake rates in strains with functioning transport systems to strains where these transporters had been knocked out by deletion of key genes. The Hg uptake into the biosensors was quantified based on the intracellular conversion of inorganic mercury (Hg(II)) to elemental mercury (Hg(0)) by the enzyme MerA. It was found that uptake of Hg from Hg-cysteine (Hg(CYS)₂) and Hg-glutathione (Hg(GSH)₂) complexes occurred at the same rate as that of inorganic complexes of Hg(II) into Escherichia coli strains with and without intact Mer transport systems. However, higher rates of Hg uptake were observed in the strain with a functioning Mer transport system. These results demonstrate that thiol-bound Hg is bioavailable to E. coli and that this bioavailability is higher in Hg-resistant bacteria with a complete Mer system than in non-resistant strains. No difference in the uptake rate of Hg from Hg(GSH)₂ was observed in E. coli strains with or without functioning glutathione transport systems. There was also no difference in uptake rates between a wildtype Bacillus subtilis strain with a functioning cystine/cysteine transport system, and a mutant strain where this transport system had been knocked out. These results cast doubt on the viability of the hypothesis that the entire Hg-thiol complex is taken up into the cell by a thiol transporter. It is more likely that the Hg in the Hg-thiol complex is transferred to a transport protein on the cell membrane and is subsequently internalized.     

Purification and characterization of an extracellular carbonic anhydrase from Pseudomonas fragi

Extracellular carbonic anhydrase was purified from Pseudomonas fragi isolated from CaCO₃ enriched soil samples. The enzyme is induced in presence of CaCO₃ and is envisaged to play an important role in bicarbonate ion transport. The 75% ammonium sulphate dialysate was purified by single step affinity chromatography with 86% yield. It is a trimeric protein having a subunit molecular weight of 31.0 kDa and was stable at pH 7.0–8.5 and temperature 35–45 °C. Lead, mercury and EDTA had an inhibitory effect on CA activity, whereas zinc, iron and cadmium increased it. The presence of esterase activity along with IC₅₀ of sulphonamides and anionic inhibitors indicated that CA from P. fragi belonged to α-class. The CA stability in presence of different salts, as well as in alkaline pH and high temperature makes it a potential candidate to be exploited for biomimetic CO₂ sequestration.     

Mercury-resistant bacterial strains Pseudomonas and Psychrobacter spp. isolated from sediments of Orbetello Lagoon (Italy) and their possible use in bioremediation processes

This study was aimed to isolate Hg-resistant bacteria from contaminated sediments of the Orbetello Lagoon in Italy and to assess their possible use as biofilms in bioremediation processes. Enrichment cultures prepared from contaminated sediments in the presence of 0.05 mM of mercury and under aerobic conditions allowed the isolation of five heterotrophic bacterial strains. 16S rDNA gene sequencing assigned the isolated strains to the genera Pseudomonas and Psychrobacter. For the first time mercury-resistant bacterial strains belonging to the genus Psychrobacter were evidenced. Minimum inhibitory concentrations in the presence of HgCl₂ and of CH₃HgCl showed high levels of resistance. EC50 values for the isolated bacterial strains in the presence of HgCl₂ and of CH₃HgCl confirmed the adaptation to the metal. Hg-resistant strains ORHg1, ORHg4 and ORHg5 showed the capacity to volatilize inorganic and organic mercury to elemental mercury, and formed biofilms on pumice particles, and were shown to play a role in the removal of mercury from sediment leachates. This study reports isolation and characterization of new Hg-resistant bacterial strains and provides novel insight into their possible use in bioremediation processes of mercury polluted sediments.     

Coupling in secondary transport Effect of electrical potentials on the kinetics of ion linked co-transport

In a previous paper kinetic equations of secondary active transport by co-transport have been derived. In the present paper these equations have been expanded by including the effect of an electrical potential difference in order to make them applicable to the more realistic systems of secondary active transport driven by the gradients of Na⁺ or H⁺. Thermodynamically an electrical potential difference is as a driving force fully exchangeable with an equivalent chemical potential difference. This is not necessarily so for the kinetics of co-transport. It is not always the same whether a given difference in electrochemical activity of the driver ion is mainly osmotic, i.e. due to difference in concentration, or electric, i.e. due to a difference in the electrochemical activity coefficient. In most cases a difference in concentration is more effective in driving co-transport than is an equivalent difference in electrical potential leading to the same difference in electrical activity. The effectiveness of the latter highly depends on the model, whether it is of the affinity type or of the velocity type, but also on whether the loaded or the unloaded carrier bears an electrical charge. With the same electrical potential difference co-transport is as a rule faster if the ternary complex rather than the empty carrier is charged. Also the “standard parameters”, (see Glossary, page 62) J_max and K_m, of the overall transport respond differently to the introduction of an electrical potential difference, depending on the model. So an electrical potential difference will mostly affect K_m if the loaded carrier is ionic, and mostly J_max if the empty carrier is ionic, provided that the mobility of the loaded carrier is greater than that of the empty one. On the other hand, distinctive criteria between affinity type and velocity type models are partly affected by an electrical potential difference. If the translocation steps of loaded and unloaded carrier are no longer rate limiting for the overall transport, electrical effects on the transport rate are bound to vanish as does the activation by co-transport.     

Calcium Transport in the Green Alga Mesotaenium caldariorum: Preliminary Characterization and Subcellular Distribution

The subcellular localization and biochemical characterization of calcium transport were studied in the unicellular green alga Mesotaenium caldariorum. Membrane fractions prepared by osmotic lysis of Mesotaenium protoplasts exhibit high rates of ATP-dependent calcium uptake. Sucrose gradient centrifugation separates two pools of activity, which display specific activities for calcium transport as high as 15 nanomoles Ca²⁺ per minute per milligram of protein. Marker enzyme analysis shows that this dual distribution of calcium transport activity is similar to that of vanadate-insensitive ATPase and pyrophosphatase, activities considered to be associated with the tonoplast. Plasma membranes, endoplasmic reticulum vesicles, mitochondrial membranes, and thylakoids band at higher densities than either calcium transport fraction. Both pools of ATP-dependent calcium uptake contain two components which are not separable on sucrose gradients but can be distinguished on the basis of inhibitor sensitivity. One component is inhibited by nigericin or trimethyltin chloride (I₅₀ values of 3 nanomolar and 4 micromolar, respectively), while the other component is vanadate sensitive (I₅₀ of 25 micromolar). These results suggest that direct Ca²⁺ transport and Ca²⁺/H⁺ antiport activities are present in both sucrose gradient fractions.     

The phosphorylation site associated with the oxidation of exogenous donors of electrons to Photosystem I

1. The Photosystem I-mediated transfer of electrons from diaminodurene, diaminotoluene and reduced 2,6-dichlorophenolindophenol to methylviologen is optimal at pH 8–8.5, where phosphorylation is also maximal. In the presence of superoxide dismutase, the efficiency of phosphorylation rises from ? 0.1 at pH 6.5 to 0.6–0.7 at pH 8–8.5, regardless of the exogenous electron donor used.2. The apparent K_m (at pH 8.1) for diaminodurene is 6·10^?4 M and for diaminotoluene is 1.2·10^?3 M. The concentrations of diaminodurene and diaminotoluene required to saturate the electron transport processes are > 2 mM and > 5 mM, respectively. At these higher electron donor concentrations the rates of electron transport are markedly increased by phosphorylation (1.5-fold) or by uncoupling conditions (2-fold).3. Kinetic analysis of the transfer of electrons from reduced 2,6-dichlorophenolindophenol (DCIPH₂) to methylviologen indicates that two reactions with very different apparent K_m values for DCIPH₂ are involved. The rates of electron flux through both pathways are increased by phosphorylation or uncoupling conditions although only one of the pathways is coupled to ATP formation. No similar complications are observed when diaminodurene or diaminotoluene serves as the electron donor.4. In the diaminodurene → methylviologen reaction, ATP formation and that part of the electron transport dependent upon ATP formation are partially inhibited by the energy transfer inhibitor HgCl₂. This partial inhibition of ATP formation rises to about 50% at less than 1 atom of mercury per 20 molecules of chlorophyll, then does not further increase until very much higher levels of mercury are added.5. It is suggested that exogenous electron donors such as diaminodurene, diaminotoluene and DCIPH₂ can substitute for an endogenous electron carrier in donating electrons to cytochrome f via the mercury-sensitive coupling site (Site I) located on the main electron-transporting chain. If this is so, there would seem to be no reason for postulating yet another coupling site on a side branch of the electron transport chain in order to account for cyclic photophosphorylation.     

Effect of dietary calcium and 1,25-(OH)2D3 on the expression of calcium transport genes in calbindin-D9k and -D28k double knockout mice

The phenotypes of calbindin-D9k (CaBP-9k) and -28k (CaBP-28k) single knockout (KO) mice are similar to wild-type (WT) mice due to the compensatory action of other calcium transport proteins. In this study, we generated CaBP-9k/CaBP-28k double knockout (DKO) mice in order to investigate the importance of CaBP-9k and CaBP-28k in active calcium processing. Under normal dietary conditions, DKO mice did not exhibit any changes in phenotype or the expression of active calcium transport genes as compared to WT or CaBP-28k KO mice. Under calcium-deficient dietary conditions, the phenotype and expression of calcium transport genes in CaBP-28k KO mice were similar to WT, whereas in DKO mice, serum calcium levels and bone length were decreased. The intestinal and renal expression of transient receptor potential vanilloid member 6 (TRPV6) mRNA was significantly decreased in DKO mice fed a calcium-deficient diet as compared to CaBP-28k KO or WT mice, and DKO mice died after 4 weeks on a calcium-deficient diet. Body weight, bone mineral density (BMD) and bone length were significantly reduced in all mice fed a calcium and 1,25-(OH)₂D₃-deficient diet, as compared to a normal diet, and none of the mice survived more than 4 weeks. These results indicate that deletion of CaBP-28k alone does not affect body calcium homeostasis, but that deletion of CaBP-9k and CaBP-28k has a significant effect on calcium processing under calcium-deficient conditions, confirming the importance of dietary calcium and 1,25-(OH)₂D₃ during growth and development.     

Transepithelial transport of hesperetin and hesperidin in intestinal Caco-2 cell monolayers

The cell permeability of hesperetin and hesperidin, anti-allergic compounds from citrus fruits, was measured using Caco-2 monolayers. In the presence of a proton gradient, hesperetin permeated cells in the apical-to-basolateral direction at the rate (J_ap → bl) of 10.43 ± 0.78 nmol/min/mg protein, which was more than 400-fold higher than that of hesperidin (0.023 ± 0.008 nmol/min/mg protein). The transepithelial flux of hesperidin, both in the presence or absence of a proton gradient, was nearly the same and was inversely correlated with the transepithelial electrical resistance (TER), indicating that the transport of hesperidin was mainly via paracellular diffusion. In contrast, the transepithelial flux of hesperetin was almost constant irrespective of the TER. Apically loaded NaN₃ or carbonyl cyanide m-chlorophenylhydrazone (CCCP) decreased the J_ap → bl of hesperetin, in the presence of proton gradient, by one-half. In the absence of a proton gradient, both J_ap → bl and J_bl → ap of hesperetin were almost the same (5.75 ± 0.40 and 5.16 ± 0.73 nmol/min/mg protein). J_bl → ap of hesperetin in the presence of a proton gradient was lower than J_bl → ap in the absence of a proton gradient. Furthermore, J_bl → ap in the presence of a proton gradient remarkably increased upon addition of NaN₃ specifically to the apical side. These results indicate that hesperetin is absorbed by transcellular transport, which occurs mainly via proton-coupled active transport, and passive diffusion. Thus, hesperetin is efficiently absorbed from the intestine, whereas hesperidin is poorly transported via the paracellular pathway and its transport is highly dependent on conversion to hesperetin via the hydrolytic action of microflora. We have given novel insight to the absorption characteristics of hesperetin, that is proton-coupled and energy-dependent polarized transport.     

Mercury detoxifying enzymes within endospores of a broad-spectrum mercury resistantBacillus pasteurii strain DR2

Bacillus pasteurii DR₂, a broad-spectrum Hg-resistant bacterial strain, exhibited delayed sporulation and less mercury volatilization in the presence of mercury compounds. However, Hg-sensitiveBacillus subtilis sporulated quickly in the presence of HgCl₂ and volatilized no mercury. Levels of Hg²⁺-reductase and organomercurial lyase in the endospores ofBacillus pasteurii DR₂ were lower than those in vegetative cells     

The effects of hydrogen ions on the kinetics of calcium transport by rat kidney mitochondria

The influence of pH on the kinetics of the initial rate of calcium uptake by isolated kidney mitochondria was studied using the ruthenium red-ethylene glycol bis(β-aminoethyl ether) N,N-tetraacetic acid quench method (K. Reed and F. Bygrave, 1975, Eur. J. Biochem.55, 497–504). In the absence of phosphate, the K_m is increased 50% and the V is decreased 57% when the pH is decreased from pH 7.4 to 7.0. Conversely, when the pH is increased to 7.8, the K_m is decreased 25% while the V is not affected. The presence of 0.1 or 0.4 mm phosphate in the incubation medium abolishes the change in K_m at a low pH while the V remains depressed by 36 and 25%, respectively. The presence of phosphate does not affect the decrease in the K_m seen with an increased medium pH. Mitochondria incubated in steady-state conditions with a medium free calcium of 0.7 μm also show significant changes in calcium exchange and distribution with pH. Two kinetic calcium pools are found in isolated mitochondria. Decreasing pH from 7.4 to 7.1 decreases mitochondria total calcium 32%, decreases the rapidly exchanging pool 28%, and depresses both the mitochondrial membrane and an intramitochondrial calcium exchange by 54 and 22%, respectively. Raising the pH to 7.7 increases both exchangeable pools (63 and 46%), and increases the mitochondrial membrane calcium exchange 44%. These results are consistent with previous studies on the influence of intracellular pH on calcium metabolism of kidney cells in which the mitochondrial pool was markedly affected by pH (R. Studer, and A. Borle, 1979, J. Membrane Biol.48, 325–341). Alterations in cellular pH may modify mitochondrial calcium transport and cellular calcium metabolism and thus affect cell functions which are calcium dependent.     

PGF2α levels in Day 8 blood plasma are increased by the presence of one or more embryos in the uterus

In cattle, the detection of very early endometrial responses is considered to be hampered by the presence of only a single embryo. Therefore, we have previously developed a model of multiple embryo transfer to circumvent this hindrance. In this work, we analysed embryo–maternal interactions in the bovine uterus on day 8 of development while comparing the presence of multiple v. single embryos using embryo transfer and artificial insemination, respectively. Concentration of proteins (β-actin, NFkB, clusterin and immunoproteosome 20S β5i subunit–i20S), by western blot, and hexoses (glucose and fructose) were measured in paired samples of uterine fluid (UF) from the same animal with and without embryos in the uterus and were compared with UF obtained after artificial insemination. Prostaglandin (PG) F₂α and PGE₂ concentrations were also analysed in blood plasma. The four proteins analysed and hexoses were unaffected by the presence of one or more embryos in the uterus. However, blood PGF₂α showed similar, significant increases with one or more embryos over cyclic animals; such changes were not observed in blood PGE₂. Although multiple embryo transfer may appear to be non-physiological, we showed that the uterus, at the very early embryonic stages, does exhibit physiological reactions. Multiple embryo transfer can, therefore, be used for studies of very early embryo–maternal interactions in vivo in monotocous species.     

Effect of prostaglandins on oviduct tone in the domestic hen in vivo

The effect of i.v. injected prostaglandins (PG) F₂α and E₂ on intraluminal pressure of the different oviductal parts (infundibulum, magnum, isthmus, uterus and vagina) was investigated in the domestic hen. PGF₂α induced only a pressure rise in all oviduct segments. Administration of PGE₂ resulted in variable changes in oviductal tone: pressure rise in the infundibulum; pressure increase often preceded by a small decrease in the magnum, isthmus and uterus; pressure decrease in the vagina and sometimes in the uterus. Simultaneous i.v. injection of both PG's induced mostly a decrease in vaginal tone. Intraluminal administration of PGF₂α or E₂ resulted only in an increase in uterine pressure.The observed effects on oviduct tone are discussed and a possible in intervention of both PG's in the mechanism of ovum transport and oviposition in the domestic hen is proposed.     

Mercury and osmoregulation in the euryhaline crab,Eriocheir sinensis

This review will focus on cases where it might be possible that the toxicity of the heavy metal mercury results from an interaction with osmoregulatory mechanisms. It is shown that mercury-induced impairment of osmoregulatory capability in the sense of severe modifications of the blood osmotic concentration is more pronounced in brachyuran decapod species adapted to dilute waters. The rationale for considering these effects is based on a comparison between mercury effects on three species of decapod crustaceans exhibiting various degrees of osmoregulation capability: the strong regulator crab Eriocheir sinensis, the weak regulator Carcinus maenas, both of them being euryhaline, and the stenohaline osmoconformer Cancer pagurus. It is established that a synergistic effect exists between salinity and HgCl₂ toxicity in euryhaline species which are hyperregulators in dilute media, that is, E. sinensis and C. maenas only. Depth study of E. sinensis as a model demonstrates that Na⁺ and Cl⁻ permeabilities of the gill epithelium is affected by mercury, as well as the Na⁺ and Cl⁻ active transport processes located at the same level. Evidences are brought showing that mercury drastically disturbs the Na⁺/K⁺ pump and the Cl⁻ channels located in the serosal baso-lateral membranes of the posterior gills.     

N,N,N′,N′-Tetramethylethylendiamine adducts of amido calcium bases - Synthesis of monomeric [(tmeda)Ca{N(SiMe3)2}2], [(tmeda)Ca{NiPr2}2], and dimeric Hauser base-type [(tmeda)Ca(tmp)(μ-I)]2 (tmp = 2,2,6,6-tetramethylpiperidide)

The metathetical reaction of calcium diiodide with KNR₂ in the presence of N,N,N′,N′-tetramethylethylendiamine yields the corresponding amido calcium bases [(tmeda)Ca(tmp)₂] (1), [(tmeda)Ca{N(SiMe₃)₂}₂] (3), and [(tmeda)Ca(NiPr₂)₂] (4) regardless of the stoichiometric ratio of the starting compounds. All compounds are highly air and moisture sensitive. Only in the case of NR₂ being a tmp group very few crystals of the Hauser base-type dimeric derivative [(tmeda)Ca(tmp)(μ-I)]₂ (2) with bridging iodide ions can be isolated. In all these calcium complexes the amides are bound terminally and contain planarily coordinated nitrogen atoms. The calcium complex [(tmeda)Ca(NiPr₂)₂] (4) is much more reactive than the lighter magnesium congener and therefore, it has to be stored below 0 °C in order to avoid decomposition reactions.