Evolution of the nonionic inverse microemulsion-acid-TEOS system during the synthesis of nanosized silica via the sol-gel process.

The cyclohexane-igepal inverse microemulsion, comprehensively established for the synthesis of silica nanoparticles in an ammonia-catalyzed sol-gel process, was alternatively studied with an acid-catalyzed sol-gel process. Tetraethyl orthosilicate (TEOS) was used as the silica precursor, while two different aqueous phases containing either HNO(3) or HCl at two different concentrations, 0.1 and 0.05 M, were examined in the presence and in the absence of NaF, a catalyst of the condensation step. The evolution of the overall reacting system, specifically hydrolysis and polycondensation of reaction intermediates, was monitored in situ by time-resolved small-angle X-ray scattering. No size variation of the inverse micelles was detected throughout the sol-gel process. Conversely, the density of the micellar core increased after a certain time interval, indicating the presence of the polycondensation product. The IR spectra of the reacting mixture were in agreement with such a hypothesis. (1)H and (13)C NMR measurements provided information on the soluble species, the surfactant, and TEOS. The TEOS consumption was well fitted by means of an exponential decay, suggesting that a first-order kinetics for TEOS transpires in the various systems examined, with rate constants dependent not only on the acid concentration but also on its nature (anion specific effect), on the presence of NaF, and on the amount of water in the core of the inverse micelle. The self-diffusion coefficients, determined by means of PGSTE NMR, proved that a sizable amount of the byproduct ethanol was partitioned inside the inverse micelles. Characterization of the final product was carried out by means of thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM), which concurrently confirmed that the silica isolated from the inverse nonionic microemulsion is not significantly different from the product of a bulk acid-catalyzed sol-gel synthesis. TEM micrographs illustrated particles with diameters smaller than the diameter of the inverse micelles as determined by SAXS, due to a shrinkage effect, in addition to nanostructured aggregates in the range 20-100 nm.

Solution microstructures of the micellar phase of Pluronic L64/SDS/water system.

Here we report on a study dealing with a self-assembling ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (Pluronic L64) and an anionic surfactant, sodium dodecyl sulfate (SDS), that in water at 25 degrees C form an interesting micellar region (L-phase). We have investigated the sequence of micelle structures in this L-phase across a wide interval of copolymer concentrations using phase diagram determination, steady shear, and NMR self-diffusion (pulsed gradient spin-echo, PGSE) experiments. In solutions which have been prepared at moderately low copolymer concentrations (ca. 20wt.% L64) we report on a transition from discrete micelles to bicontinuous aggregates on the addition of SDS. This change was mainly inferred from self-diffusion coefficient patterns (i.e., the variation of copolymers and surfactant diffusivity vs. SDS content). At midrange and at higher polymer concentrations (i.e., in the interval from 50 to 80wt.% L64) the L-phase occurred with a bicontinuous structure which was not modified by the progressive addition of SDS. Such a bicontinuous structure was identified by the comparison of self-diffusion coefficients of both cosolutes and the bulk viscosity (i.e., the behavior of zero-shear viscosity vs. SDS).

A multinuclear NMR study of [Pt0(PPh3)2(alkene)] compounds containing asymmetric olefins.

The 1H, 13C, 31P, and 195Pt NMR spectra of [Pt0(PPh3)2(eta-ABC(1) = C(2)XY)] compounds (ABC(1)= C(2)XY (1) A = B = X = Y = H; (3) A = B = X = H, Y = CN; (4) A = H, B = p-NO2-Ph, X = COOCH3, Y = CN; (5) A = H, B = Ph, X = COOCH3, Y = CN; (6) A = H, B = Ph, X = Y = CN; (7) A = H, B = OEt, X = Y = CN), where X and Y are electronacceptor substituents, and the 1H spectrum of [Pt0(PPh3)2(eta2-C60)] (2) are reported together with extended analyses and assignments, based also on the ring current effect of the olefin phenyl in (4-6). Deviations from first order in the 13C spectra allowed the determination of the relative signs of the coupling constants J(P(1), C) and J(P(2), C) of the alkene and of the triphenylphosphine carbons. Best fit simulation of the phosphine C ipso spectrum provided also the 13C isotopic shift on phosphorus for (1). These compounds are characterised by strong differences between the two platinum-phosphorus coupling constants in the case of asymmetric olefins (3-7). The chemical shifts of alkene C(1) and C(2) indicate notable polarisation of the olefin after complexation, while the 1J(Pt, C(1)) and 1J(Pt, C(2)) values are in agreement with a stronger interaction of Pt with C(1) than with C(2). These findings together with the trend of 195Pt chemical shifts confirm the important role played by back-donation in the bonding of platinum(0)-olefin compounds.

63Cu-31P coupling constants and 63Cu quadrupole couplings from 31P CP/MAS spectra of copper (I)--phosphine complexes with aryldithiocarboxylates or benzoate.

Magic-angle spinning 31P NMR spectra of solid [CuS2C-Ph(PPh3)2] 1, [{CuS2C-pT}4(PPh3)2] 2, [{CuS2C-Ph}4(PPh3)2] 3. [CuS2C-Ph(dppm)]2 4 and [CuO2C-Ph(dppm)]2 5, (T = tolyl, dppm = bis(diphenylphosphino)methane) were obtained at 109.6 MH2. They consist of distorted quartets from non-equivalent phosphorus atoms and provide approximate values of the indirect spin-spin coupling constant J[63Cu,31P], that are indicative of the covalency of the dithiocarboxylate-copper bonding. The spacing distortions are related to a number of molecular and structural parameters and thereby allow an estimation of the copper quadrupole coupling constant e2qQ/h which, as expected, is smaller for tetra-coordinated (1, 2, 3 and 4) than for tri-coordinated (5) copper sites. The spectrum of 2 has been successfully simulated (including the isotope effects from the less abundant 65Cu isotope) using the full theory for calculation of the spin eigenfunctions of the quadrupolar nucleus.

Synthesis and antimycobacterial activity of some 4-pyridinecarboxyamidrazone derivatives.

A series of N1-aryliden-4-pyridinecarboxyamidrazone derivatives was prepared. Some of the synthesized compounds showed interesting in vitro antimycobacterial activity against some strains of Mycobacterium and clinical isolates of Mycobacterium tuberculosis.

Proximal impact deposits at the Cretaceous-Tertiary boundary in the Gulf of Mexico: a restudy of DSDP Leg 77 Sites 536 and 540.

Restudy of Deep Sea Drilling Project Sites 536 and 540 in the southeast Gulf of Mexico gives evidence for a giant wave at Cretaceous-Tertiary boundary time. Five units are recognized: (1) Cenomanian limestone underlies a hiatus in which the five highest Cretaceous stages are missing, possibly because of catastrophic K-T erosion. (2) Pebbly mudstone, 45 m thick, represents a submarine landslide possibly of K-T age. (3) Current-bedded sandstone, more than 2.5 m thick, contains anomalous iridium, tektite glass, and shocked quartz; it is interpreted as ejecta from a nearby impact crater, reworked on the deep-sea floor by the resulting tsunami. (4) A 50-cm interval of calcareous mudstone containing small Cretaceous planktic foraminifera and the Ir peak is interpreted as the silt-size fraction of the Cretaceous material suspended by the impact-generated wave. (5) Calcareous mudstone with basal Tertiary forams and the uppermost tail of the Ir anomaly overlies the disturbed interval, dating the impact and wave event as K-T boundary age. Like Beloc in Haiti and Mimbral in Mexico, Sites 536 and 540 are consistent with a large K-T age impact at the nearby Chicxulub crater.

Synthesis and antimycobacterial activity of some 2-pyridinecarboxyamidrazone derivatives.

A series of N1-aryliden-2-pyridincarboxyamidrazone derivatives was prepared. Some of the synthesized compounds showed interesting in vitro antimycobacterial activity against some strains of Mycobacterium and clinical isolates of Mycobacterium tuberculosis.

Tektite-bearing, deep-water clastic unit at the Cretaceous-Tertiary boundary in northeastern Mexico.

The hypothesis of Cretaceous-Tertiary (K-T) boundary impact on Yucatán, Mexico, predicts that nearby sites should show evidence of proximal impact ejecta and disturbance by giant waves. An outcrop along the Arroyo el Mimbral in northeastern Mexico contains a layered clastic unit up to 3 m thick that interrupts a biostratigraphically complete pelagic-marl sequence deposited at more than 400 m water depth. The marls were found to be unsuitable for determining magnetostratigraphy, but foraminiferal biostratigraphy places the clastic unit precisely at the K-T boundary. We interpret this clastic unit as the deposit of a megawave or tsunami produced by an extraterrestrial impact. The clastic unit comprises three main subunits. (1) The basal "spherule bed" contains glass in the form of tektites and microtektites, glass spherules replaced by chlorite-smectite and calcite, and quartz grains showing probable shock features. This bed is interpreted as a channelized deposit of proximal ejecta. (2) A set of lenticular, massive, graded "laminated beds" contains intraclasts and abundant plant debris, and may be the result of megawave backwash that carried coarse debris from shallow parts of the continental margin into deeper water. (3) At the top, several thin "ripple beds" composed of fine sand are separated by clay drapes; they are interpreted as deposits of oscillating currents, perhaps a seiche. An iridium anomaly (921 +/- 23 pg/g) is observed at the top of the ripple beds. Our observations at the Mimbral locality support the hypothesis of a K-T impact on nearby Yucatán.

Iridium profile for 10 million years across the Cretaceous-Tertiary boundary at Gubbio (Italy).

The iridium anomaly at the Cretaceous-Tertiary (KT) boundary was discovered in the pelagic limestone sequence at Gubbio on the basis of 12 samples analyzed by neutron activation analysis (NAA) and was interpreted as indicating impact of a large extraterrestrial object at exactly the time of the KT mass extinction. Continuing controversy over the shape of the Ir profile at the Gubbio KT boundary and its interpretation called for a more detailed follow-up study. Analysis of a 57-meter-thick, 10-million-year-old part of the Gubbio sequence using improved NAA techniques revealed that there is only one Ir anomaly at the KT boundary, but this anomaly shows an intricate fine structure, the origin of which cannot yet be entirely explained. The KT Ir anomaly peaks in a 1-centimeter-thick clay layer, where average Ir concentration is 3000 parts per trillion (ppt); this peak is flanked by tails with Ir concentrations of 20 to 80 ppt that rise above a background of 12 to 13 ppt. The fine structure of the tails is probably due in part to lateral reworking, diffusion, burrowing, and perhaps Milankovitch cyclicity.

Geological and geochemical record of 3400-million-year-old terrestrial meteorite impacts.

Beds of sand-sized spherules in the 3400-million-year-old Fig Tree Group, Barberton Greenstone belt, South Africa, formed by the fall of quenched liquid silicate droplets into a range of shallow-to deep-water depositional environments. The regional extent of the layers, their compositional complexity, and lack of included volcanic debris suggest that they are not products of volcanic activity. The layers are greatly enriched in iridium and other platinum group elements in roughly chondritic proportions. Geochemical modeling based on immobile element abundances suggests that the original average spherule composition can be approximated by a mixture of fractionated tholeiitic basalt, komatiite, and CI carbonaceous chondrite. The spherules are thought to be the products of large meteorite impacts on the Archean earth.

The Precursor of the Cretaceous-Tertiary Boundary Clays at Stevns Klint, Denmark, and DSDP Hole 465A.

Results of detailed mineralogical, chemical, and oxygen isotope analyses of the clay minerals and zeolites from two Cretaceous-Tertiary (K/T) boundary regions, Stevns Klint, Denmark, and Deep Sea Drilling Project (DSDP) Hole 465A in the north central Pacific Ocean, are presented. In the central part of the Stevns Klint K/T boundary layer, the only clay mineral detected by x-ray diffraction is a pure smectite with > 95 percent expandable layers. No detrital clay minerals or quartz were observed in the clay size fraction in these beds, whereas the clay minerals above and below the boundary layer are illite and mixed-layer smectite-illite of detrital origin as well as quartz. The mineralogical purity of the clay fraction, the presence of smectite only at the boundary, and the delta(18)O value of the smectite (27.2 +/- 0.2 per mil) suggest that it formed in situ by alteration of glass. Formation from impact rather than from volcanic glass is supported by its major element chemistry. The high content of iridium and other siderophile elements is not due to the cessation of calcium carbonate deposition and resulting slow sedimentation rates. At DSDP Hole 465A, the principal clay mineral in the boundary zone (80 to 143 centimeters) is a mixed-layer smectite-illite with >/=90 percent expandable layers, accompanied by some detrital quartz and small amounts of a euhedral authigenic zeolite (clinoptilolite). The mixed-layer smectite-illite from the interval 118 to 120 centimeters in the zone of high iridium abundance has a very low rare earth element content; the negative cerium anomaly indicates formation in the marine environment. This conclusion is corroborated by the delta(18)O value of this clay mineral (27.1 +/- 0.2 per mil). Thus, this mixed-layer smectite-illite formed possibly from the same glass as the K/T boundary smectite at Stevns Klint, Denmark.

Impact theory of mass extinctions and the invertebrate fossil record.

There is much evidence that the Cretaceous-Tertiary boundary was marked by a massive meteorite impact. Theoretical consideration of the consquences of such an impact predicts sharp extinctions in many groups of animals precisely at the boundary. Paleontological data clearly show gradual declines in diversity over the last 1 to 10 million years in various invertebrate groups.Reexamination of data from careful studies of the best sections shows that, in addition to undergoing the decline, four groups (ammonites, cheilostomate beyozoans, brachiopods, and bivalves) were affected by sudden truncations precisely at the iridium anomaly that marks the boundary. The paleontological record thus bears witness to terminal-Cretaceous extinctions on two time scales: a slow decline unrelated to the impact and a sharp truncation synchronous with and probably caused by the impact.

The end of the cretaceous: sharp boundary or gradual transition?

Evidence indicates that the Cretaceous-Tertiary boundary is very sharp, and, within the limits of resolution, it is apparently synchronous at the various boundary localities. Arguments to the contrary, particularly those of Officer and Darke, are shown to invalid.

Iridium anomaly approximately synchronous with terminal eocene extinctions.

An iridium anomaly has been found in coincidence with the known microtektite level in cores from Deep Sea Drilling Project site 149 in the Caribbean Sea. The iridium was probably not in the microtektites but deposited simultaneously with them; this could occur if the iridium was deposited from a dust cloud resulting from a bolide impact, as suggested for the anomaly associated with the Cretaceous-Tertiary boundary. Other workers have deduced that the microtektites are part of the North American strewn tektite field, which is dated at about 34 million years before present, and that the microtektite horizon in deep-sea cores is synchronous with the extinction of five radiolarian species. Mass extinctions also occur in terrestrial mammals within 4 million years of this time. The iridium anomaly and the tektites and microtektites are supportive of a major bolide impact about 34 million years ago.

Extraterrestrial cause for the cretaceous-tertiary extinction.

Platinum metals are depleted in the earth's crust relative to their cosmic abundance; concentrations of these elements in deep-sea sediments may thus indicate influxes of extraterrestrial material. Deep-sea limestones exposed in Italy, Denmark, and New Zealand show iridium increases of about 30, 160, and 20 times, respectively, above the background level at precisely the time of the Cretaceous-Tertiary extinctions, 65 million years ago. Reasons are given to indicate that this iridium is of extraterrestrial origin, but did not come from a nearby supernova. A hypothesis is suggested which accounts for the extinctions and the iridium observations. Impact of a large earth-crossing asteroid would inject about 60 times the object's mass into the atmosphere as pulverized rock; a fraction of this dust would stay in the stratosphere for several years and be distributed worldwide. The resulting darkness would suppress photosynthesis, and the expected biological consequences match quite closely the extinctions observed in the paleontological record. One prediction of this hypothesis has been verified: the chemical composition of the boundary clay, which is thought to come from the stratospheric dust, is markedly different from that of clay mixed with the Cretaceous and Tertiary limestones, which are chemically similar to each other. Four different independent estimates of the diameter of the asteroid give values that lie in the range 10 +/- 4 kilometers.

The Colossi of Memnon Revisited: Recent research has established the source of the stone of the two 720-ton statues at Thebes.

The only areas that are likely to have furnished the original stone for the Colossi of Memnon are near Cairo (Gebel el Ahmar), Aswan, and possibly Silsileh. Neutron activation analysis of samples from the colossi shows them to be distinctly different from samples obtained from the three known quarries near Aswan and from the quarries near Silsileh and Edfu, but very similar to samples obtained from Gebel el Ahmar. Petrographic analysis of colossi and quarry samples also provides strong evidence that the colossi came from Gebel el Ahmar. The blocks used by the engineers of Septimius Severus to reconstruct the north colossus were shown by neutron activation analysis to have originated from a deposit other than Gebel el Ahmar. The composition of these blocks conformed with samples taken from the quarries 8 and 9 km north of Edfu (the quartzite deposit closest to Thebes) and from the Aswan quarries. Petrographic analysis associated these reconstruction blocks with Edfu but not with Aswan. Neutron activation analysis of other artifacts in the area of the colossi indicates that they also came from Cairo rather than Aswan.