A first-order liquid-liquid phase transition in phosphorus

First-order structural phase transitions are common in crystalline solids, whereas first-order liquid-liquid phase transitions (that is, transitions between two distinct liquid forms with different density and entropy) are exceedingly rare in pure substances. But recent theoretical and experimental studies have shown evidence for such a transition in several materials, including supercooled water and liquid carbon. Here we report an in situ X-ray diffraction observation of a liquid-liquid transition in phosphorus, involving an abrupt, pressure-induced structural change between two distinct liquid forms. In addition to a known form of liquid phosphorus--a molecular liquid comprising tetrahedral P4 molecules--we have found a polymeric form at pressures above 1 GPa. Changing the pressure results in a reversible transformation from the low-pressure molecular form into the high-pressure polymeric form. The transformation is sharp and rapid, occurring within a few minutes over a pressure range of less than 0.02 GPa. During the transformation, the two forms of liquid coexist. These features are strongly suggestive of a first-order liquid-liquid phase transition.

Chaetopterus photoprotein: crystallization and cofactor requirements for bioluminescence.

The Chaetopterus photoprotein has been isolated in an amorphous form (molecular weight, 120,000) whlich in (NH(4))(2)SO(4) sollutionl converts to a crystalline form (molecular weight, 184,000) having the same specific light-emittinig activity; quantum yields are 0.0093 and 0.0143, respectively. Two new cofactor reqluirements have been separated fronm impure extracts: a macromnolecule resembling a nucleoprotein, and a lipid-like substance.

Cypridina bioluminescence: light-emitting oxyluciferin-luciferase complex.

Fluorescence of Cypridina oxyluciferin is greatly enhanced when it is bound to luciferase; the spectrum is thereby shifted, so that it corresponds precisely to the emission spectrum characteristic of the bioluminescentoxidation of luciferin. Thus the oxyluciferin-luciferase complex is the lightemitter. The binding is equimolar, with dissociation constant K(D) equal to 3x 10(-7) mole per liter. The molecular weight of the luciferase, according to three different methods, is between 52,000 and 57,000; molecular activities of luciferase for the bioluminescence reaction and for the hydrolysis of oxy-luciferin are 1600 and 2 per minute, respectively.

Baddeleyite-Type High-Pressure Phase of TiO2.

A high-pressure phase of TiO(2), which had been observed by shock-wave experiments and remained unresolved, has been studied by in situ x-ray diffraction. The single phase was formed at 20 gigapascals and 770 degrees C with the use of sintered-diamond multianvils; it has the same structure as baddeleyite, the stable phase of ZrO(2) at ambient conditions. The coordination number of Ti increases from six to seven across the rutile to baddeleyite transition, and the volume is reduced by approximately 9 percent.

The Phase Boundary Between agr- and beta-Mg2SiO4 Determined by in Situ X-ray Observation.

The stability of Mg(2)SiO(4), a major constituent in the Earth's mantle, has been investigated experimentally by in situ observation with synchrotron radiation. A cubic-type high-pressure apparatus equipped with sintered diamond anvils has been used over pressures of 11 to 15 gigapascals and temperatures of 800 degrees to 1600 degrees C. The phase stability of alpha-Mg(2)SiO(4) and beta-Mg(2)SiO(4) was determined by taking account of the kinetic behavior of transition. The phase boundary between alpha-Mg(2)SiO(4) and beta-Mg(2)SiO(4) is approximated by the linear expression P = (9.3 +/- 0.1) + (0.0036 +/- 0.0002)T where P is pressure in gigapascals and T is temperature in degrees Celsius.

Preparation and handling of aequorin solutions for the measurement of cellular Ca2+.

Main characteristics of the various types of aequorin presently available for measuring cellular Ca2+, i.e. heterogeneous aequorin, isoaequorins, recombinant aequorin, fluorescein-labeled aequorin and semi-synthetic aequorins, are summarized. Basic techniques of preparing and handling the solutions of those aequorins for measuring Ca2+, including such techniques as concentrating aequorin solutions, freeze-drying, changing buffer composition, and the regeneration of active aequorin, are described.

Light-emitting properties of recombinant semi-synthetic aequorins and recombinant fluorescein-conjugated aequorin for measuring cellular calcium.

15 kinds of recombinant semi-synthetic aequorins and a recombinant fluorescein-conjugated aequorin were prepared and their properties in Ca(2+)-triggered luminescence were studied. The semi-synthetic aequorins showed a wide range of Ca(2+)-sensitivity. The luminescence intensity of a high-sensitivity type (hcp-aequorin) was greater than 10(4)-times that of a low-sensitivity type (n-aequorin) at pCa 6.0-6.5. The fluorescein-conjugated aequorin exhibited fluorescence in addition to the Ca(2+)-triggered luminescence, thus it can be used to visualize the diffusion and distribution of aequorin in cells. The data obtained, particularly the Ca(2+)-sensitivity curves, are useful in selecting a suitable semi-synthetic aequorin for an experiment.

Secretional luciferase of the luminous shrimp Oplophorus gracilirostris: cDNA cloning of a novel imidazopyrazinone luciferase(1).

The deep-sea shrimp Oplophorus gracilirostris secretes a luciferase that catalyzes the oxidation of coelenterazine to emit blue light. The luciferase (M(r) approx. 106000) was found to be a complex composed of 35 kDa and 19 kDa proteins, and the cDNAs encoding these two proteins were cloned. The expression of the cDNAs in bacterial and mammalian cells indicated that the 19 kDa protein, not the 35 kDa protein, is capable of catalyzing the luminescent oxidation of coelenterazine. The primary sequence of the 35 kDa protein revealed a typical leucine-rich repeat sequence, whereas the catalytic 19 kDa protein shared no homology with any known luciferases including various imidazopyrazinone luciferases.

A preliminary phantom study on a proposed model for quantification of renal planar scintigraphy.

A method for estimation of the absolute renal activity within background activity in renal planar scintigraphy will be presented. This method corrects for oversubtraction of background activity with consideration of background activity of the kidney volume, and employs the depth-independent buildup factor (DIBF) method for the correction of attenuation and scatter of photons. This method requires the depth and thickness of the organ and the thickness of background for a background activity correction. The transmission factor (TF) for a volume source is derived from integrating TF for a thin source over the thickness of the organ for the DIBF method. To validate this method, phantom studies with various uniform background activity concentrations were performed and the data were compared with conventional background subtraction that do not consider the organ's volume. The results showed that with the conventional background subtraction method at all depth activity was underestimated with errors of 5%-30% for organ/background concentration ratios of 5-40, while this method estimated the true count rate with errors of less than 5%. More accurate quantifications of renal functions such as renal uptake, glomerular filtration rate (GFR) and renogram may be obtained by this proposed method on the planar images.

Development of macromolecular Sn(II) complex for preparation of 99Tcm radiopharmaceuticals.

Macromolecular Sn(II) complex (R-Sn) was developed using a chelating resin containing aminophosphonic acid groups as a reducing agent of 99Tcm(VII) in the preparation of 99Tcm radiopharmaceuticals. Since Sn(II) was bonded strongly to the resin by chelation, release of Sn from R-Sn was rarely observed in saline solution. 99Tcm labelling with a yield greater than 90% was performed by mixing R-Sn, 99Tcm pertechnetate solution and a ligand, such as human serum albumin and diethylenetriamine pentaacetic acid, for a short time. The 99Tcm radiopharmaceuticals were almost free from Sn(II) and the reducing activity of R-Sn was quite stable despite long-term storage without any special care.

Isolation and properties of the luciferase stored in the ovary of the scyphozoan medusa Periphylla periphylla.

Bioluminescence of the medusa Periphylla is based on the oxidation of coelenterazine catalyzed by luciferase. Periphylla has two types of luciferase: the soluble form luciferase L, which causes the exumbrellar bioluminescence display of the medusa, and the insoluble aggregated form, which is stored as particulate material in the ovary, in an amount over 100 times that of luciferase L. The eggs are especially rich in the insoluble luciferase, which drastically decreases upon fertilization. The insoluble form could be solubilized by 2-mercaptoethanol, yielding a mixture of luciferase oligomers with molecular masses in multiples of approximately 20 kDa. Those having the molecular masses of 20 kDa, 40 kDa, and 80 kDa were isolated and designated, respectively, as luciferase A, luciferase B, and luciferase C. The luminescence activities of Periphylla luciferases A, B, and C were 1.2 approximately 4.1 x 10(16) photon/mg. s, significantly higher than any coelenterazine luciferase known, and the quantum yields of coelenterazine catalyzed by these luciferases (about 0.30 at 24 degrees C) are comparable to that catalyzed by Oplophorus luciferase (0.34 at 22 degrees C), which has been considered the most efficient coelenterazine luciferase until now. Luciferase L (32 kDa) could also be split by 2-mercaptoethanol into luciferase A and an accessory protein (approx. 12 kDa), as yet uncharacterized. Luciferases A, B, and C are highly resistant to inactivation: their luminescence activities are only slightly diminished at pH 1 and pH 11 and are enhanced in the presence of 1 approximately 2 M guanidine hydrochloride; but they are less stable to heating than luciferase L, which is practically unaffected by boiling.

Versatile type miniature diamond anvil high-pressure cell.

A miniature diamond anvil high-pressure cell 42 mm in diameter, 18 mm thick, and 150 g in weight has been constructed. The cell is loaded into a piston-cylinder type pressing device with an alignment mechanism and compressed to a desired pressure. After the pressure is clamped by three screws, the cell part is taken out. Thereby, in spite of the small and simple cell, pressure can be generated easily and steadily up to 200 kbar. Because the cell is small and light enough to be mounted on a usual goniometer head, and has large openings towards both the top and bottom, it can widely be used as a versatile apparatus for research at high pressure.

Transrectal portal scintigraphy with I123 iodoamphetamine in liver diseases.

Using transrectal portal scintigraphy with I123 iodoamphetamine, we calculated the portosystemic shunt index and investigated the portal hemodynamics in patients with various liver diseases. The shunt index tended to increase in the order of chronic hepatitis, primary biliary cirrhosis, compensated liver cirrhosis, and decompensated liver cirrhosis. An increase in the stage of esophageal varices (assessed endoscopically) also tended to be associated with an increase in the shunt index. The shunt index correlated significantly with both the ICG test and the spleen index. Accordingly, measurement of the shunt index by this method appeared to accurately reflect the existence and severity of portosystemic shunting, and to be of value in the evaluation of portal circulatory abnormalities. However, no clear differences were found in the shunt index following hepatic arterial injection chemotherapy for hepatocellular carcinoma, or endoscopic injection sclerotherapy for esophageal varices.

Usefulness of reinjection image for evaluating viable myocardium in the infarcted zone on exercise thallium-201 SPECT.

Reinjection images were obtained in 23 patients with myocardial infarction by the additional injection of 37 MBq of thallium-201 after obtaining 4 hour delayed images on exercise thallium-201 SPECT (TSPECT). A redistribution index (RI) was derived of the changes in perfusion defects between immediate and 4 hour delayed images as well as immediate and reinjection images on polar bull's eye maps. The RI of reinjection images (46 +/- 27%) was significantly greater than that of 4 hour delayed images (26 +/- 26%) in patients with myocardial infarction (p less than 0.01). Significant redistribution after reinjection occurred in 4 of 9 patients (44%) without significant redistribution on 4 hour delayed images. Improvement in redistribution on reinjection images correlated significantly to the small extent of coronary artery disease and collateral development. The appearance of redistribution from 4 hour delayed imaging to reinjection imaging also might reflect the function of collateral development in the resting state in patients without significant redistribution on 4 hour delayed images. It has been demonstrated that underestimated viable myocardium on 4 hour delayed images in the infarcted zone can be better assessed on reinjection images. This reinjection technique is recommended in patients with no or partial redistribution on 4 hour delayed images.

A new method for crosstalk correction in simultaneous dual-isotope myocardial imaging with Tl-201 and I-123.

We have developed a new method of crosstalk correction in simultaneous dual-isotope imaging with Tl-201 and I-123 by using crosstalk ratios and a blurring filter. Single isotope myocardial studies (10 for Tl-201 and 7 for I-123) were performed with a dual energy window acquisition mode and two low energy general-purpose collimators. Then two planar images acquired with dual energy windows for a Tl-201 line source and an I-123 line source were obtained to measure line spread functions (LSFs) and crosstalk ratios for each image. The line source experiments showed that the LSFs for the Tl-201 imaging window from the single Tl-201 source were very similar to those for the I-123 imaging window from the single Tl-201 source, but the LSFs for the Tl-201 imaging window from the single I-123 source had broad shapes which differed from those for the I-123 imaging window from the single I-123. To obtain accurate I-123 crosstalk images in the Tl-201 imaging window from the I-123 images in the I-123 imaging window, we designed a low-pass blurring filter. In 7 clinical I-123 MIBG studies, I-123 window images processed with this filter became very similar to the Tl-201 window image from the single I-123 source. The method proposed in this study can accurately correct the crosstalk in dual isotope studies with Tl-201 and I-123 and is easily applicable to conventional gamma camera systems with any dual energy window acquisition mode.

MR findings of hypoxic damage of the bilateral striate cortices: a case report.

MR imaging of a patient with cortical blindness revealed areas of abnormal signal bilaterally in the lateral putamen and the striate cortices. The coronal T2-weighted image clearly demonstrated the selective involvement of the bilateral striate cortices. The differential diagnosis and the vulnerability of the striate cortex are discussed.

Single photon emission computed tomography in children with idiopathic seizures.

Single photon emission computed tomography (SPECT) with N-isopropyl-p[123I]-iodoamphetamine (IMP), X-ray computed tomography (X-CT), and magnetic resonance imaging (MRI) were performed in 20 children with idiopathic seizures. In children with idiopathic seizures, SPECT could detect the abnormal sites at the highest rate (45%) compared with CT (10%) and MRI (12%), but the abnormal sites on SPECT correlated poorly with the foci on electroencephalograph (EEG). Idiopathic epilepsy with hypoperfusion on SPECT was refractory to treatment and was frequently associated with mental and/or developmental retardation. Perfusion defects on SPECT scans probably affect the development and maturation of the brain in children.

[Diagnosis of pheochromocytoma using 131I-MIBG scintigraphy].

131I-MIBG scintigraphy was performed on 18 patients with pheochromocytoma and 25 patients with essential hypertension. In comparison of grade of 131I-MIBG accumulation in various organs the heart accumulation of pheochromocytoma group was significantly lower than that of essential hypertension group. And between the positive and false negative accumulation group of pheochromocytoma reverse relationship was observed between the heart and tumor. The results of 131I-MIBG scintigraphy for pheochromocytoma included 78% sensitivity, 100% specificity, and 90% accuracy. False negative accumulation of tumors were shown at 6 lesions in 4 cases. On the bases of CT and operative findings, false negative accumulation was observed not only in very small tumors, but also in large cystic tumors with a small amount of tumor tissue or totally hemorrhagic necrosis within the tumor.