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Pd(0.213)Cd(0.787) and Pd(0.235)Cd(0.765) structures: their long c axis and composite crystals, chemical twinning, and atomic site preferences.

We present single-crystal studies of Pd(0.213)Cd(0.787) and Pd(0.235)Cd(0.765), synchrotron powder studies of Pd(1-x)Cd(x), 0.755> or =x> or =0.800, and LDA-DFT and extended Hückel (eH) calculations on these or related phases. The two single-crystal structures have a, b, and c axis lengths of 9.9013(7), 14.0033(10), 37.063(24) and 9.9251(3), 14.0212(7), 60.181(3) A, respectively and they crystallize in the space groups Ccme and F2mm, respectively (solved as (3+1)-dimensional crystals their most convenient superspace group is Xmmm(00gamma)s00). The structures have two different structural components each with their own separate axis parameters. Powder data shows that the ratio of these separate axes (S/L) varies from 1.615 to 1.64, values near the golden mean (1.618). For Pd(0.213)Cd(0.787), different Pd and Cd site occupancies lead to variation in the R factor from 2.6-3.6 %. The site occupancy pattern with the lowest R factor (among the 26 820 variants studied) is the exact site occupancy pattern predicted by LDA-DFT parameterized eH Mulliken charge populations. The phases can be understood through a chemical twinning principle found in gamma-brass, the parent structure for the above phases (a relation with the MgCu(2) Laves phase is also noted). This twinning principle can be used to account for Cd and Pd site preferences. At the same time there is a clean separation among the Cd and Pd atoms for the two separate chain types at height b=0 and 1/2. These results indicate that Cd:Pd stoichiometry plays a role in phase stability.

Cadmium↗

Comparative studies on the electrical properties of the H+ translocating ATPase and pyrophosphatase of the vacuolar-lysosomal compartment.

The electrical properties of the vacuolar-lysosomal H+ pumps were studied by direct measurement of the pump currents using the whole-cell configuration of the patch-clamp technique. Both pumps, the proton-translocating ATPase and pyrophosphatase, when activated by MgATP or inorganic Mg pyrophosphate (MgPP(i)), transport protons into the vacuole and polarize the membrane potential (positive inside the vacuole). Accumulation of protons in the lumen of vacuole vesicles was monitored by absorbance changes of the pH probe, acridine orange. The electrochemical gradient provided by both the ATPase and pyrophosphatase stimulates effectively the uptake of various metabolites such as malate, citrate and sucrose. The maximal current density produced by the ATPase was about 2.5 microA/cm2 and about 0.5 microA/cm2 for the pyrophosphatase. K(m)ATP was 0.6 mM; K(m)PPi was 15-20 microM with progressive inhibition above 150 microM. At a cytoplasmic pH of 7.5 both enzymes were capable of pumping protons against a 10,000-fold concentration gradient (pH 3.5 inside the vacuole). Proton current produced by the ATPase was blocked reversibly by extravacuolar NO(3)- only.

Adenosine Triphosphate↗

Effect of pH on the microhardness of renal calculi.

The effects of synthetic urine environments of pH 4, 6, and 9.5 on the microhardness of renal calculi have been investigated. Tests were made, using both Vickers and Knoop indenters, on three compositions of calculi: 100% calcium oxalate monohydrate (whewellite), 100% uric acid, and 98% magnesium ammonium phosphate hexahydrate (struvite) mixed with 2% carbonate apatite. Whewellite calculi hardness was lowered, relative to (dry) values by 45-55% when saturated with a solution of pH 9.5. Exposure to lower pH conditions was not as effective in lowering hardness in this case. Struvite calculi hardness was lowered by 41-52% compared to the dry hardness and uric acid calculi hardness decreased by 25-36%, compared to dry hardnesses. For uric acid stones the reduction in hardness did not depend on pH within the range of pH values investigated. For struvite stones, acid pH conditions appear to give an increased softening, compared to other pH values.

Biomechanical Phenomena↗

Fatigue of kidney stones with heterogeneous microstructure subjected to shock-wave lithotripsy.

In this article a theoretical framework is developed for the mechanics of kidney stones with an isotropic, random microstructure--such as those comprised of cystine or struvite. The approach is based on a micromechanical description of kidney stones comprised of crystals in a binding matrix. Stress concentration functions are developed to determine load sharing of the particle phase and the binding matrix phase. Measurements have shown the inclusions to be considerably harder than the binder; consequently, loading of a stone leads to higher stresses in the inclusions than in the binder. As an illustration of the theory, the fatigue of kidney stones subject to shock-wave lithotripsy is considered. Stress concentration functions are used to construct fatigue-life estimates for each phase, as a function of the volume fraction and of the mechanical properties of the constituents, as well as the loading from SWL. The failure of the binding matrix, or of the particulate phase, is determined explicitly in a model for the accumulation of distributed damage. The theory can be used to assess the importance of microscale heterogeneity on the comminution of renal calculi, and to estimate the number of cycles to failure in terms of measurable material properties.

Biomechanical Phenomena↗

Physicochemical action of potassium-magnesium citrate in nephrolithiasis.

Effect of potassium-magnesium citrate on urinary biochemistry and crystallization of stone-forming salts was compared with that of potassium citrate at same dose of potassium in five normal subjects and five patients with calcium nephrolithiasis. Compared to the placebo phase, urinary pH rose significantly from 6.06 +/- 0.27 to 6.48 +/- 0.36 (mean +/- SD, p less than 0.0167) during treatment with potassium citrate (50 mEq/day for 7 days) and to 6.68 +/- 0.31 during therapy with potassium-magnesium citrate (containing 49 mEq K, 24.5 mEq Mg, and 73.5 mEq citrate per day). Urinary pH was significantly higher during potassium-magnesium citrate than during potassium citrate therapy. Thus, the amount of undissociated uric acid declined from 118 +/- 61 mg/day during the placebo phase to 68 +/- 54 mg/day during potassium citrate treatment and, more prominently, to 41 +/- 46 mg/day during potassium-magnesium citrate therapy. Urinary magnesium rose significantly from 102 +/- 25 to 146 +/- 37 mg/day during potassium-magnesium citrate therapy but not during potassium citrate therapy. Urinary citrate rose more prominently during potassium-magnesium citrate therapy (to 1027 +/- 478 mg/day from 638 +/- 252 mg/day) than during potassium citrate treatment (to 932 +/- 297 mg/day). Consequently, urinary saturation (activity product) of calcium oxalate declined significantly (from 1.49 x 10(-8) to 1.03 x 10(-8) M2) during potassium-magnesium citrate therapy and marginally (to 1.14 x 10(-8) M2) during potassium citrate therapy.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗

Size distribution characteristics of mineral phase in renal stones.

The size distribution of the mineral phases in three renal stones (whewellite, struvite, and whitlockite) was determined using a particle-counting technique after removal of the organic matrix. The multisized crystallites of the investigated stones revealed close similarity in size distribution characteristics. Whewellite size parameters were in good agreement with the parameters of calcium oxalate monohydrate crystals formed in the kidneys of rats injected with L-4-hydroxyproline. However, these parameters differed significantly from the values calculated from the size distribution of calcium oxalate crystals voided in the urine of recurrent stone formers. The data obtained suggest that critical size distribution characteristics may be instrumental in causing the mineral phase to agglomerate and adopt a close packing in renal stones.

Animals↗

Oxidative degradation of hydrocortisone in presence of attapulgite.

Degradation of hydrocortisone in attapulgite suspensions was monitored by high-pressure liquid chromatography and UV spectrophotometry. The rate of oxidative degration of hydrocortisone was accelerated significantly in the presence of attapulgite. In addition, degradation appeared to be composed of two apparent first-order reactions rather than the single apparent first-order degradation reaction observed for hydrocortisone solutions. However, the same degradation products were obtained in both hydrocortisone solutions and attapulgite suspensions, indicating that interaction with attapulgite did not alter the degradation pathway. Kinetic and adsorption studies suggested that hydrocortisone is adsorbed weakly by attapulgite and undergoes oxidative degradation, which is catalyzed by adsorbed iron oxides or hydroxides as well as by structural ferric iron at the clay surface. Since clay minerals generally contain surface ferric iron, the potentiala for accelerating the oxidative degradation of drugs should be considered whenever clays and drugs are combined.

Bentonite↗

Preliminary experience with the pulsed dye laser for treatment of urolithiasis.

We report our initial experience using the pulsed dye laser in 26 patients with urolithiasis. The patients ranged in age from 27 to 82 years; 11 patients were female and 15 were male. Of the 26 patients, 4 stones were in the kidney, 21 were in the ureter, and one was in the bladder. Surgical time ranged from 32 to 130 minutes. All patients were treated under spinal or general anesthesia. The size of ureteral stones ranged from 0.2 to 1.5 cm, and the renal stones 3.0 to 4.0 cm. Chemical analysis of the stones was not available on all patients, but when available, chemical analysis revealed the stones to be calcium monohydrate, calcium dihydrate, or struvite. The use of the Candela miniscope in 11 patients permitted access without ureteral dilation. In 19 patients, ureteral stents were placed. One patient suffered a ureteral perforation. Success was defined as adequate disintegration of the stone for passage of the fragments without the necessity of a secondary procedure. Using this criterion, 22 of 26 patients were successfully treated for an overall success rate of 85%.

Adult↗

Detection of loop-mediated isothermal amplification reaction by turbidity derived from magnesium pyrophosphate formation.

The loop-mediated isothermal amplification (LAMP) is a novel nucleic acid amplification method that uses only one type of enzyme. One of the characteristics of the LAMP method is its ability to synthesize extremely large amount of DNA. Accordingly, a large amount of by-product, pyrophosphate ion, is produced, yielding white precipitate of magnesium pyrophosphate in the reaction mixture. Judging the presence or absence of this white precipitate allows easy distinction of whether nucleic acid was amplified by the LAMP method. Since an increase in the turbidity of the reaction mixture according to the production of precipitate correlates with the amount of DNA synthesized, real-time monitoring of the LAMP reaction was achieved by real-time measurement of turbidity.

Base Sequence↗

Mapping in three dimensions of regions in a catalytic RNA protected from attack by an Fe(II)-EDTA reagent.

The accessibility of the ribose groups in the phosphodiester chain of M1 RNA, the catalytic subunit of ribonuclease P from Escherichia coli, has been probed with an Fe(II)-EDTA reagent when the RNA is alone in solution, when it is in a complex with a tRNA precursor substrate, and when it is in the holoenzyme complex with its cofactor, C5 protein. The regions found to be protected under these various conditions, as well as those previously identified in other chemical probing experiments, have been mapped on a three-dimensional working model of M1 RNA and are generally compatible with the previously proposed placement of the substrate on the enzyme and with previous data and inferences regarding the interactions of C5 protein with M1 RNA. On the basis of the accessibilities of the C(4') atoms, refinements have been introduced in the model to accommodate the Fe(II)-EDTA protection data. The protein cofactor makes contact with several helical regions of the catalytic RNA on the opposite side of the surface to which substrates bind.

Bacterial Proteins↗

Pyrophosphate synthesis from phospho(enol)pyruvate catalyzed by precipitated magnesium phosphate with "enzyme-like" activity.

The enzyme-like kinetic properties of precipitated magnesium phosphate as a catalyst for formation of pyrophosphate (PPi) from phospho(enol)pyruvate (PEP) are described. This synthesis occurs at a low temperature (37 degrees C) and represents a model that may help us understand the relevance to chemical evolution of minerals as ancient catalysts whose functions could have been taken over by contemporary enzymes. An insoluble Pi.Mg matrix was formed in a medium with 80% of the water replaced by dimethyl sulfoxide as a way of simulating conditions in a drying pond. Phospho(enol)pyruvate adsorbs onto the Pi.Mg surface according to a Langmuir isotherm, and the PEP concentration dependence of PPi formation follows a Michaelian-like function. A yield of 33% for transformation of the initially adsorbed PEP into PPi was attained after 4 days of incubation with equimolecular concentrations of Pi, MgCl2, and PEP. The magnesium concentration dependence for Pi and Mg precipitation, for adsorption of PEP onto solid Pi.Mg, and for PPi formation showed complex cooperative behavior. These results taken as a whole lead to the conclusion that the Pi.Mg surface not only provides a reactant for PPi formation but also catalyzes the reaction.

Diphosphates↗

Glycosaminoglycans and struvite calculi.

Glycosaminoglycans (GAGs) are suspended in urine and are present on tissue surfaces in the urinary tract. Consequently, they have the potential to influence any pathological disorder in this environment, including urinary tract infections by Proteus mirabilis and struvite (NH4MgPO4.6H2(0)) urolithiasis. Although GAGs, suspended in urine, may inhibit the formation of other types of calculus minerals, no such effect has been reported in struvite calculi. Nevertheless, GAGs are a major component of the organic matrix of all types of urinary calculi. In contrast, there is evidence that the GAG layer on the bladder surface may act as a defence mechanism against infection by inhibiting bacterial adhesion. More studies are needed to elucidate fully the role of GAGs in urinary infections and struvite urolithiasis.

Glycosaminoglycans↗

Management of complex renal calculi.

The treatment of small renal pelvic and ureteric calculi can be performed with relative safety and efficacy using lithotripsy or an endourological method. There remains however, a proportion of stones that are resistant to these methods because of their anatomical position, physical composition or sheer size. To these stones must be applied a treatment strategy using the variety of techniques to their maximum advantage. This article aims to review the accumulated experience on the management of these more complex urinary calculi.

Calcium Phosphates↗