Guy Matzen

Heavy elements in urinary stones

The presence and role of heavy metals in urinary stones is debated. We investigated the distribution of trace heavy metals in 78 calculi of well-defined composition by means of microfluorescence X analysis using synchrotron radiation. Seven elements were identified, the most abundant being Zn and Sr which together accounted for 91% of the heavy metal content of stones. The other heavy metals were Fe, Cu, Rb, Pb and Se. Zn and Sr were virtually confined to calcium-containing stones, whereas only trace amounts were found in uric acid or cystine stones. Among calcium stones, Zn and Sr were more abundant in calcium phosphate than in calcium oxalate stones and, in the latter, in weddellite than in whewellite stones. Fe, Cu and Rb were much less abundant and also found mainly in calcium stones. Pb was significantly less abundant than in previous studies, thus suggesting a rarefaction of Pb in the environment, and appreciable amounts of Se were found only in cystine stones. In conclusion, the preponderance of Zn and Sr, both bivalent ions, in calcium-containing stones suggests a substitution process of calcium by metal ions with similar charge and radius rather than a contribution of the metals to stone formation. Further studies are needed to examine the relationships between urine concentration in calcium or other solutes and the amount of Zn and Sr in calcium stones.

Relationships Between Carbonation Rate of Carbapatite and Morphologic Characteristics of Calcium Phosphate Stones and Etiology

OBJECTIVES To examine the significance of the carbonation rate (CR) in carbonated apatite (carbapatite [CA]) stones and its relationships with the morphologic characteristics of CA and etiology. CA stones without struvite can result from metabolic disorders or urinary tract infection, but the latter etiology is still debated. Infection stones caused by urea-splitting bacteria are made of CA admixed with struvite and exhibit a high CO(3)(2-)/PO(4)(3-) ratio (CR). However, little is known as to the significance of the CR of CA in the absence of struvite in idiopathic calcium phosphate stones. METHODS We studied 39 urinary calculi mainly composed of CA without struvite. Of the 39 patients, 13 had a past or present history of urinary tract infection, 24 had hypercalciuria, and 2 had medullary sponge kidney. The stones were examined by Fourier transform infrared spectroscopy and scanning electron microscopy. The presence of amorphous carbonated calcium phosphate or whitlockite was also considered. RESULTS The CR of CA was 14% +/- 9%. On scanning electron microscopy, the CA particles appeared as spherules of 4.5 +/- 3.0 mum in diameter and were significantly larger in females than in males. In 16 cases, scanning electron microscopy showed bacterial imprints. In these calculi, the CR was significantly greater (22% +/- 7%) than in those without a visible bacterial imprint (8% +/- 5%, P < .0001). Amorphous carbonated calcium phosphate was found in 15 of 16 stones (93.8%) with imprints and in none of the 23 stones without imprints (P < .0001). CONCLUSIONS A close relationship was observed between the presence of bacterial imprints, indicative of past or current urinary tract infection, and both the presence of amorphous carbonated calcium phosphate (or whitlockite) and a high CR of CA.

Examination of whewellite kidney stones by scanning electron microscopy and powder neutron diffraction techniques

# 2009 International Union of Crystallography Printed in Singapore – all rights reserved Kidney stones made of whewellite, i.e. calcium oxalate monohydrate, exhibit various morphological aspects. The crystalline structure of whewellite at the atomic scale was revisited through a single-crystal neutron study at room temperature using a four-circle automated diffractometer. The possible relationships between the various morphological types of whewellite stones and their structural characteristics were examined at the mesoscopic scale by the use of scanning electron microscopy and at the nanometric scale by powder neutron diffraction. All types of whewellite stones displayed a similar structure at the nanometric scale. However, significant differences were found at the mesoscopic scale. In particular, the crystallites in kidney stones resulting from a genetic hyperoxaluria exhibited a peculiar structure. There was a close relationship between stone morphology and crystallite organization at the mesoscopic level and the effectiveness of extracorporeal shockwave lithotripsy.

Structural Investigations of Glass Ceramics in the Ga2S3―GeS2―CsCl System

Transparent glass ceramics have been prepared in the Ga(2)S(3)-GeS(2)-CsCl pseudoternary system using appropriate heat treatment time and temperature. In situ X-ray diffraction at the heat treatment temperature and (133)Cs and (71)Ga solid-state nuclear magnetic resonance have been performed in function of annealing time to understand the crystallization process. Both techniques have evidenced the nucleating agent role played by gallium with the formation of Ga(2)S(3) nanocrystals. On the other hand, cesium is incorporated very much later into the crystallites during the ceramization. Moreover, the addition of CsCl, which is readily integrated into the glassy network, permits us to shift the optical band gap toward shorter wavelength. Thus, new glass ceramics transmitting in the whole visible range up to 11.5 mum have been successfully synthesized from the (Ga(2)S(3))(35)-(GeS(2))(25)-CsCl(40) base glass composition.

Diffraction techniques and Vibrational spectroscopy opportunities to characterise bones

From a histological point of view, bones that allow body mobility and protection of internal organs consist not only of different organic and inorganic tissues but include vascular and nervous elements as well. Moreover, due to its ability to host different ions and cations, its mineral part represents an important reservoir, playing a key role in the metabolic activity of the organism. From a structural point of view, bones can be considered as a composite material displaying a hierarchical structure at different scales. At the nanometre scale, an organic part, i.e. collagen fibrils and an inorganic part, i.e. calcium phosphate nanocrystals are intimately mixed to assure particular mechanical properties.

Highly Transparent BaAl4O7 Polycrystalline Ceramic Obtained by Full Crystallization from Glass

Transparent polycrystalline ceramics are an emerging class of photonic quality materials competing with single crystal technology for a diverse range of applications including high-energy lasers, scintillating devices, optical lenses, and transparent armour. Polycrystalline ceramics offer several advantages, particularly in the fabrication of complex shapes and large-scale industrial production, and enable greater and more homogenous doping of optically active ions than is possible in single crystals. A limited number of either cubic or nanocrystalline transparent polycrystalline ceramics are known, but require complex and time-consuming synthetic approaches. Here, we show for the fi rst time that fully dense transparent polycrystalline ceramics can be simply obtained by direct and complete crystallization from glass. This is demonstrated for the previously unreported composition, BaAl 4 O 7 , which exhibits two orthorhombic polymorphs with micrometer grain size, both optically transparent in the visible range. This innovative synthetic route to transparent polycrystalline ceramics should facilitate the discovery of new, cost-effective chemical methods for transparent ceramic applications. Conventional optically transparent single crystal materials are widely used in numerous photonic applications. However, these materials face several technological and economical challenges, including a restricted list of appropriate single crystal compounds, limitations on the type and level of chemical doping, and mechanical and manufacturing requirements for large and complex physical shapes. Many of these obstacles can be avoided through the use of ceramic materials, which afford a wider range

Absence of Bacterial Imprints on Struvite-containing Kidney Stones: A Structural Investigation at the Mesoscopic and Atomic Scale

OBJECTIVE Bacterial imprints are always observed on highly carbonated apatite kidney stones but not struvite kidney stones. Struvite and carbonated apatite stones with a high CO(3)(2-)/PO(4)(3-) rate are believed to develop from infections, but their structural differences at the mesoscopic scale lack explanation. METHODS We investigated 17 urinary calculi composed mainly of struvite or carbonated apatite by Fourier transform infrared, scanning electron microscopy, and powder neutron diffraction techniques. RESULTS Carbonated apatite but not struvite stones showed bacterial imprints. If the same stone contained both carbonated apatite and struvite components, bacterial imprints were observed on the carbonated apatite but not the struvite part. Moreover, neutron powder diffraction experiments revealed the crystal size of struvite stones were larger than that of carbonated apatite stones (250 ± 50 vs 50 nm). CONCLUSION Bacterial imprints may appear more easily on kidney stones with small nanocrystals, such as carbonated apatite than with large nanocrystals, such as struvite. This approach may help identify bacteria contributing to stone formation, perhaps with negative results of urine culture.

Long-lasting luminescent ZnGa2O4:Cr3+ transparent glass-ceramics

Highly transparent ZnGa2O4 glass-ceramic materials are elaborated via a simple heat treatment of a 55SiO2–5Na2O–17ZnO–23Ga2O3 parent glass composition, which presents nanoscale spinodal phase separation. This optimized glass-ceramic exhibits 50 wt% of ZnGa2O4 nanocrystals showing a homogeneous and tuneable size. To describe the crystallization process, the glass and glass-ceramic nanostructures are studied by high resolution scanning transmission electron microscopy analysis coupled with in situ high temperature X-ray diffraction and optical measurements. From these results, an original mechanism is proposed to explain the crystallization process occurring in a spinodal phase separated glass. Remarkably, red long-lasting luminescence arising from the entire sample volume is observed in the Cr3+ doped transparent glass-ceramics, opening the route to a wider range of performing applications for this famous zinc gallate persistent phosphor.

Synthesis and structure determination of CaSi1/3B2/3O8/3, a new calcium borosilicate

This article reports on the identification, synthesis, and in-situ structure determination of a new crystalline calcium borosilicate compound of composition CaSi(1/3)B(2/3)O(8/3). Synthesis was carried out by complete crystallization on annealing from a corresponding glassy composition in the widely studied CaO-SiO2-B2O3 ternary system. The crystallographic structure was determined ab initio using electron diffraction information and the charge flipping algorithm performed on synchrotron and neutron powder diffraction data collected in situ at high temperature. CaSi(1/3)B(2/3)O(8/3) is found to crystallize in the Pna2(1) (no. 33) orthorhombic space group, with a = 12.1025(4) Å, b = 5.2676(1) Å, c = 3.7132(1) Å, and V = 236.71(1) Å(3) at 650 °C. Solid-state (29)Si and (11)B NMR experiments have confirmed the existence of finite chains along the c axis, formed by corner-sharing SiO4 tetrahedra and BO3 units. Silicon and boron species share a crystallographic site, and the Si/B distribution induces different possible arrangements of the chains which are discussed in light of DFT calculations. At room temperature, the existence of a superstructure, resulting from the ordering within nanoscale domains, was explored by transmission electron microscopy.

Therapy modifies cystine kidney stones at the macroscopic scale. Do such alterations exist at the mesoscopic and nanometre scale

With an incidence of 1:7000 births, cystinuria, the most frequent cause of stone formation among genetic diseases, represents a major medical problem. Twentyfive cystine stones randomly selected from cystinuric patients were investigated. From a crystallographic point of view, cystine stones are composed of micrometre size crystallites, which are made up of an aggregation of nanocrystals. Through scanning electron microscopy, the morphology and size of the crystallites have been described, while the size of the nanocrystals was investigated by means of powder neutron diffraction. Powder neutron diffraction analysis and/or scanning electron microscopy examination of cystine stones provide evidence that usual alkalinization by sodium bicarbonate associated with high diuresis significantly reduces the size of both nanocrystals and crystallites, while for other treatments, including alkalinizing drugs and thiol derivatives, the data suggest mainly changes in the topology of crystallites. Alkalinization with sodium bicarbonate affects cystine kidney stones at the mesoscopic and nanoscopic scales, while other medical treatments only alter their surface. Such an approach may help to assess the interaction between drugs and cystine stones in cystinuric patients.