Radiocarbon: analysis of inorganic carbon of fossil bone and enamel

Carbon dioxide from calcium carbonate in fossil bone can be selectively separated from carbon dioxide in bone apatite by hydrolyzing the sample first in acetic acid and then in hydrochloric acid. Radiocarbon analyses of the inorganic carbon dioxide in three samples of known age clearly show calcium carbonate in fossil bone to be secondary and the carbonate of bone apatite to be indigenous and suitable for dating in some cases. Agreement between dates on collagen-bone apatite pairs increases the level of confidence.     

Supramolecular assembly of amelogenin nanospheres into birefringent microribbons

Although both tooth enamel and bone are composed of organized assemblies of carbonated apatite crystals, enamel is unusual in that it does not contain collagen nor does it remodel. Self-assembly of amelogenin protein into nanospheres has been recognized as a key factor in controlling the oriented and elongated growth of carbonated apatite crystals during dental enamel biomineralization. We report the in vitro formation of birefringent microribbon structures that were generated through the supramolecular assembly of amelogenin nanospheres. These microribbons have diffraction patterns that indicate a periodic structure of crystalline units along the long axis. The growth of apatite crystals orientated along the c axis and parallel to the long axes of the microribbons was observed in vitro. The linear arrays (chains) of nanospheres observed as intermediate states before the microribbon formation give an important indication as to the function of amelogenin in controlling the oriented growth of apatite crystals during enamel mineralization.     

Stabilizing isopeptide bonds revealed in gram-positive bacterial pilus structure

Many bacterial pathogens have long, slender pili through which they adhere to host cells. The crystal structure of the major pilin subunit from the Gram-positive human pathogen Streptococcus pyogenes at 2.2 angstroms resolution reveals an extended structure comprising two all-beta domains. The molecules associate in columns through the crystal, with each carboxyl terminus adjacent to a conserved lysine of the next molecule. This lysine forms the isopeptide bonds that link the subunits in native pili, validating the relevance of the crystal assembly. Each subunit contains two lysine-asparagine isopeptide bonds generated by an intramolecular reaction, and we find evidence for similar isopeptide bonds in other cell surface proteins of Gram-positive bacteria. The present structure explains the strength and stability of such Gram-positive pili and could facilitate vaccine development.     

促释磷肥的结构特征及其有效性机理研究

【目的】揭示促释磷肥结构特征与磷素有效性的内在联系,探讨促释磷肥的有效性量化测定方法。【方法】采用连续浸提和乙酸-乙酸钠测活性磷法,通过再活化手段及光谱学技术从持续活化能力及理化结构特征方面揭示促释磷肥的有效性机理。【结果】木质素磺酸钠处理能显著提高磷矿粉的水溶性磷和活性磷含量,4种促释磷肥的8次累积水溶性磷含量分别是对应磷矿粉的14.0、5.6、8.8和5.1倍;且乙酸-乙酸钠测得的活性磷与未处理磷矿粉相比,提高了9.8%—93.1%。红外光谱和X-衍射分析结果表明,木质素磺酸钠对磷矿粉磷素的促释作用具有持续性,能有效改变磷矿粉本身的化学成键结构,促使难溶的或枸溶Ca-P键转化为活性高的H2PO42-,降低磷灰石结晶程度,提高其有效性。【结论】促释处理能持续促进难溶性或枸溶性磷向活性磷转化,采用连续浸提和乙酸-乙酸钠测活性磷法能够对促释效果进行评价。     

Bond selectivity in silicon film growth

Hydrogen atoms can selectively eliminate strained bonds that form during the growth of amorphous silicon films. By periodically interrupting the growth and exposing the grown material to hydrogen, the film composition can be varied continuously from a non-equilibrium amorphous structure to that of a crystalline solid. Furthermore, by tuning the hydrogen exposure it is possible to discriminate between Si-Si bonds formed on different substrates, thereby allowing substrate-selective growth. The evolution of the film structure during hydrogen exposure is directly observed by scanning tunneling microscopy, and a model describing the role of hydrogen is presented.     

Lepidocrocite, an apatite mineral, and magnetic in teeth of chitons (Polyplacophora)

X-ray diffraction patterns show that the mature denticles of three extant chiton species are composed of the mineral lepidocrocite and an apatite mineral, probably francolite, in addition to magnetite. Each of the three minerals forms a discrete microarchitectural unit of the chiton denticles. This is the first indication that lepidocrocite is precipitated by marine organisms and an apatite mineral by chitons.     

Structure of the DNA-Eco RI endonuclease recognition complex at 3 A resolution

The crystal structure of the complex between Eco RI endonuclease and the cognate oligonucleotide TCGCGAATTCGCG provides a detailed example of the structural basis of sequence-specific DNA-protein interactions. The structure was determined, to 3 A resolution, by the ISIR (iterative single isomorphous replacement) method with a platinum isomorphous derivative. The complex has twofold symmetry. Each subunit of the endonuclease is organized into an alpha/beta domain consisting a five-stranded beta sheet, alpha helices, and an extension, called the "arm," which wraps around the DNA. The large beta sheet consists of antiparallel and parallel motifs that form the foundations for the loops and alpha helices responsible for DNA strand scission and sequence-specific recognition, respectively. The DNA cleavage site is located in a cleft that binds the DNA backbone in the vicinity of the scissile bond. Sequence specificity is mediated by 12 hydrogen bonds originating from alpha helical recognition modules. Arg200 forms two hydrogen bonds with guanine while Glu144 and Arg145 form four hydrogen bonds to adjacent adenine residues. These interactions discriminate the Eco RI hexanucleotide GAATTC from all other hexanucleotides because any base substitution would require rupture of at least one of these hydrogen bonds.     

A stable bicyclic compound with two Si=Si double bonds

In contrast to carbon, silicon does not readily form double bonds, and compounds containing silicon-silicon double bonds can usually be stabilized only by protection with bulky substituents. We have isolated a silicon analog of spiropentadiene 1, a carbon double-ring compound that has not been isolated to date. In the crystal structure of tetrakis[tri(t-butyldimethylsilyl)silyl]spiropentasiladiene 2, a substantial deviation from the perpendicular arrangement of the two rings is observed, and the silicon-silicon double bonds are shown to be distorted. Spectroscopic data indicate pronounced interaction between two remote silicon-silicon double bonds in the molecule. Silicon-silicon bonds may be more accessible to synthesis than previously assumed.     

Uranium distributions in archeologic ceramics: dating of radioactive inclusions

Small mineral grains (10 to 50 micrometers) of high uranium concentration (100 to 3000 parts per million) were located in polished sections of eight potsherds from Cyprus, England, Greece, and Mexico by induced fission-track mapping. Most of the grains were identified as zircons or apatites by a microprobe attachment to a scanning electron microscope. The advantages in using such radioactive grains for thermoluminescence dating and alpha-recoil track dating are discussed.     

Apatite: Origin of Blue Color

The optical absorption and emission spectra of natural blue apatite are similar enough to spectra of synthetic compounds containing MnO(4)(-3) to conclude that the blue color of natural apatite results from the presence of this ion.     

Structure of the lambda complex at 2.5 A resolution: details of the repressor-operator interactions

The crystal structure of a complex containing the DNA-binding domain of lambda repressor and a lambda operator site was determined at 2.5 A resolution and refined to a crystallographic R factor of 24.2 percent. The complex is stabilized by an extensive network of hydrogen bonds between the protein and the sugar-phosphate backbone. Several side chains form hydrogen bonds with sites in the major groove, and hydrophobic contacts also contribute to the specificity of binding. The overall arrangement of the complex is quite similar to that predicted from earlier modeling studies, which fit the protein dimer against linear B-form DNA. However, the cocrystal structure reveals important side chain-side chain interactions that were not predicted from the modeling or from previous genetic and biochemical studies.     

Crystal structure of the 1: 1 complex of 5-fluorouracil and 9-ethylhypoxanthine

9-Ethylhypoxanthine and 5-fluorouracil form a 1 : 1 crystalline complex. The structure of this complex has been solved by x-ray diffraction analysis. The molecules crystallize in a monoclinic lattice and form a sheet structure in which pairs of fluorouracil molecules are held together by two hydrogen bonds. The 9-ethylhypoxanthine residues fill up the rest of the molecular sheet by forming single hydrogen bonds with each uracil pair.     

甲烷泄露背景下碳酸盐岩的形成及其地球化学特征

甲烷泄露背景下形成的碳酸盐岩,特征上明显区别于正常海相碳酸盐岩。冷泉碳酸盐岩、震旦纪的盖帽碳酸盐岩均被认为是甲烷泄露背景下的产物,其碳同位素值都出现强烈的负漂移。研究认为,成岩中的碳源于天然气水合物分解产生的甲烷。冷泉碳酸盐岩与盖帽碳酸盐岩在结构、构造及矿物组分上很相似。对甲烷泄露背景下的碳酸盐岩的外观构造、岩石矿物特征、地球化学特征进行了分析,并阐述了这类碳酸盐岩的特征与其形成背景、过程、条件之间的关系。     

Hydrogen as a Probe of Semiconductor Surface Structure: The Ge(111)-c(2 x 8) Surface

Hydrogen can be used as an effective probe of the structure of semiconductor surfaces. Such surfaces consist of bonds with varying degrees of bond strain, and hydrogen can react with each selectively depending on the reaction conditions. This selectivity is derived from a reduced barrier to reaction associated with strained bonds. In this manner, hydrogen can be used to pick apart the surface one bond type at a time, thereby revealing the structure of even complex multilayer reconstructions. This method is used to directly show that the rest-layer of the Ge(111)-c(2 x 8) surface has a bulk structure.     

Interplay of intra- and intermolecular H-bonding in a progressively solvated macrocyclic peptide

Studying solvation of a large molecule on an atomic level is challenging because of the transient character and inhomogeneity of hydrogen bonding in liquid water. We studied water clusters of a protonated macrocyclic decapeptide, gramicidin S, which were prepared in the gas phase and then cooled to cryogenic temperatures. The experiment spectroscopically tracked fine structural changes of the clusters upon increasing the number of attached water molecules from 1 to 50 and distinguished vibrational fingerprints of different conformers. The data indicate that only the first two water molecules induce a substantial change of the gramicidin S structure by breaking two intramolecular noncovalent bonds. The peptide structure remains largely intact upon further solvation, reflecting the interplay between the strong intramolecular and weaker intermolecular hydrogen bonds.     

Anomeric bond-character in the pyranose sugars

Evidence from determinations of crystal structure relating to the shortening of carbon-oxygen bonds in the anomeric position in pyranose sugars is presented. There is a high degree of probability that the C(1)-O(1) bond is shortened by about 0.04 A relative to the other C-O single-bond lengths, except in the case of an axially oriented glycosidic group where there is evidence of a distinction between the two ring C-O bonds.     

Calcareous septa formed in snail shells by larvae of snail-killing flies

Larvae of 13 species of Pherbellia and Colobaea that feed in exposed aquatic snails uitilize a product of the Malpighian tubules before they pupate to form a plate-like structure within the shell or to reinforce the anterior end of the puparium. The substance is partly calcium carbonate, and carbonic anhydrase may be involved in its production.     

重庆岩溶区上覆土壤的粒度分布特征及成因指示

对重庆武隆岩溶区五个土壤剖面的粒度特征进行了分析,并将其粒度参数、粒度曲线、结构参数散点图等与各种沉积环境下的沉积物粒度特征进行对比,发现研究区样品的粒度特征与河流相沉积物、湖泊沉积物、坡积物等物质的粒度特征差异较大;与黄土高原红粘土、黄土古土壤、镇江下蜀土的粒度特征存在相似性,但仍有一定差异;与贵州碳酸盐岩上覆堆积物的粒度特征有较为一致的特性.根据五个土壤剖面的粒度特征推测,其沉积过程中溶蚀作用占主导,与先前风化形成该土层的原岩层性质有关,并有一定风成成因,同时还与坡面流水有一定关联.     

木材酸性液化条件下苯酚的作用机理

论述了酸性条件下木材液化中苯酚的作用机理.苯酚作为亲核试剂,引起了木材组分一些主要化学键的断裂,使得木材组分大分子降解为小分子;苯酚作为反应试剂,与其中一些降解生成的小分子反应生成具有酚类结构的化合物;苯酚作为溶剂,使生成的酚类结构化合物溶解,并减缓或阻止了已生成的活性小分子之间的缩聚反应.催化剂酸提供质子(H )以及酸性环境,使化学键的断裂更为容易,同时也改变了液化反应途径.     

Imaging powders with the atomic force microscope: from biominerals to commercial materials

Atomically resolved images of pressed powder samples have been obtained with the atomic force microscope (AFM). The technique was successful in resolving the particle, domain, and atomic structure of pismo clam (Tivela stultorum) and sea urchin (Strongylocentrotus purpuratus) shells and of commercially available calcium carbonate (CaCO(3)) and strontium carbonate (SrCO(3)) powders. Grinding and subsequent pressing of the shells did not destroy the microstructure of these materials. The atomic-resolution imaging capabilities of AFM can be applied to polycrystalline samples by means of pressing powders with a grain size as small as 50 micrometers. These results illustrate that the AFM is a promising tool for material science and the study of biomineralization.