Nitrogen K-edge X-ray adsorption near-edge structure spectroscopy of chemically adsorbed ammonia gas on clay minerals and the 15N/14N-nitrogen isotopic fractionation.

Ammonia (NH3) is a simple and essential nitrogen carrier in the universe. Its adsorption on mineral surfaces is an important step in the synthesis of nitrogenous organic molecules in extraterrestrial environments. The nitrogen isotopic ratios provide a useful tool for understanding the formation processes of N-bearing molecules. In this study, adsorption experiments were conducted using gaseous NH3 and representative clay minerals. The strongly adsorbed NH3 was 15N-enriched in a state of chemical equilibrium between the adsorption and desorption on the siliceous host surface. The nitrogen K-edge X-ray adsorption near-edge structure spectroscopy study revealed that these initial ammonia gases were chemically adsorbed as ammonium ions (NH4+) on clay minerals.

Chemical evolution of primordial salts and organic sulfur molecules in the asteroid 162173 Ryugu.

Samples from the carbonaceous asteroid (162173) Ryugu provide information on the chemical evolution of organic molecules in the early solar system. Here we show the element partitioning of the major component ions by sequential extractions of salts, carbonates, and phyllosilicate-bearing fractions to reveal primordial brine composition of the primitive asteroid. Sodium is the dominant electrolyte of the salt fraction extract. Anions and NH4+ are more abundant in the salt fraction than in the carbonate and phyllosilicate fractions, with molar concentrations in the order SO42- > Cl- > S2O32- > NO3- > NH4+. The salt fraction extracts contain anionic soluble sulfur-bearing species such as Sn-polythionic acids (n < 6), Cn-alkylsulfonates, alkylthiosulfonates, hydroxyalkylsulfonates, and hydroxyalkylthiosulfonates (n < 7). The sulfur-bearing soluble compounds may have driven the molecular evolution of prebiotic organic material transforming simple organic molecules into hydrophilic, amphiphilic, and refractory S allotropes.

Soluble organic molecules in samples of the carbonaceous asteroid (162173) Ryugu.

The Hayabusa2 spacecraft collected samples from the surface of the carbonaceous near-Earth asteroid (162173) Ryugu and brought them to Earth. The samples were expected to contain organic molecules, which record processes that occurred in the early Solar System. We analyzed organic molecules extracted from the Ryugu surface samples. We identified a variety of molecules containing the atoms CHNOS, formed by methylation, hydration, hydroxylation, and sulfurization reactions. Amino acids, aliphatic amines, carboxylic acids, polycyclic aromatic hydrocarbons, and nitrogen-heterocyclic compounds were detected, which had properties consistent with an abiotic origin. These compounds likely arose from an aqueous reaction on Ryugu's parent body and are similar to the organics in Ivuna-type meteorites. These molecules can survive on the surfaces of asteroids and be transported throughout the Solar System.

Synchrotron µ-XRF mapping analysis of trace elements in in-situ cultured Japanese red coral, Corallium japonicum.

Precious corals belong to the family Coralliidae (Cnidaria, Octocorallia), and their axis, which consists of high magnesian calcium carbonate, has long been used in jewelry. With its low growth rate and long lifespan, precious coral is a representative taxon of the vulnerable marine ecosystem. Due to years of overfishing, coral fishery has become a controversial issue. To estimate the growth rate and clarify the uptake process of trace elements in relation to the growth of the carbonate axis, Japanese red coral (Corallium japonicum) was cultured at a depth of 135 m off Takeshima Island, Kagoshima, Japan for 98 months and analyzed by microscopic X-ray fluorescence/soft X-ray photoabsorption (µ-XRF/XAS) speciation mapping. The growth rate was estimated to be 0.37 mm/year in diameter, and 10-11 growth rings were observed in a cross section of the axis. This estimated growth-rate value is the first ever to be obtained from the in-situ culture of Japanese precious coral. The fluctuation in water temperature near the in-situ-culture site was recorded for part of the culture period and then compared with the changes in the growth ring and the distribution of trace elements in a cross section of the coral axis during the same period. When the water temperature was increasing, the growth ring was light in color, sulfur and phosphorus concentrations were low, and magnesium was high. Conversely, a dark band in the growth ring, high sulfur and phosphorus, and low magnesium concentrations were observed when the water temperature was decreasing. In a cross section of the coral axis, the distribution of sulfur and magnesium from the center to the surface corresponded, respectively, to dark and light bands in the annual growth ring. Sulfur concentration was high in the dark band and low in the light band, while magnesium was negatively correlated with sulfur.

Control of Sequential MTO Reactions through an MFI-Type Zeolite Membrane Contactor.

A membrane for controlling methanol-to-olefin (MTO) reactions was developed, which featured an MFI-type zeolite membrane (Si/Al = 25) that was synthesized on a porous α-alumina substrate using a secondary growth method. Here, the H2/SF6 permeance ratios were between 150 and 450. The methanol conversion rate was 70% with 38% ethylene selectivity and 28% propylene selectivity as determined using a cross-flow membrane contactor. In order to improve the olefin selectivity of the membrane, the MFI zeolite layer (Si/Al = ∞) was coated on an MFI-type zeolite membrane (Si/Al = 25). Using this two-layered membrane system, the olefin selectivity value increased to 85%; this was 19% higher than the value obtained during the single-layer membrane system.

Rapid Purification of Alkali and Alkaline-earth Elements for Isotope Analysis (δ 7Li, δ 26Mg, 87Sr/86Sr, and δ 88Sr) of Rock Samples Using Borate Fusion Followed by Ion Chromatography with a Fraction Collector System.

For the rapid, easy, and safe purification of alkali and alkaline-earth elements from rock samples for stable isotope analysis, we developed a semi-automated, high-throughput procedure using borate fusion and an ion chromatography system equipped with a fraction collector. This HF-free procedure for the decomposition of silicate rock samples can be performed in a short time without isotope fractionation; the purification procedure enables the collection of baseline-separated peaks of multiple target elements and the complete removal of interference matrices from reagents and samples. The accuracy of this procedure was verified by confirming the correspondence of stable isotopic values of Li, Mg, Sr (δ7Li, δ26Mg, δ88Sr) and radiogenic isotopic values of Sr (87Sr/86Sr) to previously reported values in various geochemical reference materials in which the concentration range of Li was 7.78 - 86.6 ng g-1, that of Mg was 0.02 - 26.9%, and that of Sr was 178 - 7240 ng g-1. These results demonstrate that this procedure, which allows for the concurrent multi-isotope analysis of alkali and alkaline-earth elements in the same sample, is applicable to a wide variety of sample types.

Quantitative analysis of underivatized amino acids in the sub- to several-nanomolar range by ion-pair HPLC using a corona-charged aerosol detector (HPLC-CAD).

The separation and quantification of underivatized naturally occurring amino acids (AAs) by high-performance liquid chromatography (HPLC) is advantageous for reducing preparation time, running costs, and analytical errors, and is compatible with the isolation of intact AAs. This study establishes and validates an analytical method for the separation and quantification of underivatized AAs and taurine (Tau) in the sub- to several-nanomolar range (ca. 0.1-1.6 nmol) by optimizing ion-pair HPLC coupled to a corona charged aerosol detector (corona CAD). Chromatographic separation of 19 AAs and Tau was achieved using a porous graphite carbon (PGC) column and nonafluoropentanoic acid (NFPA) as a volatile ion-pair reagent. The response of the corona CAD to the AAs was highly dependent on the eluate composition, whereas these response factors were similar for AAs in eluate with similar compositions. Regression curves and coefficients (r2) >0.998 were obtained for plots of injection amount versus peak area, except for Arg which co-eluted with a background peak. On the other hand, all plots of injection amount versus peak height regressed to curves with r2 > 0.997. Repeat quantification based on peak area showed lower relative standard deviations (RSDs) (typically better than 5%) than those based on peak height. The present method is useful for quantifying AAs from proteins and Tau in the sub- to several-nanomolar range without derivatization, and constant repeatability can be maintained by quantification using peak areas.

Lithium, magnesium and sulfur purification from seawater using an ion chromatograph with a fraction collector system for stable isotope measurements.

We describe the mass descrimination and validation of an offline method for purification of Li, Mg and S with an ion chromatograph coupled to an automated fraction collector for use prior to stable isotope measurements. Significant sub-fraction mass fractionation was observed for both the Li and the Mg stable isotope ratios. The lighter Li and heavier Mg isotopes were preferentially retained by the column, resulting in 7Li/6Li and 26Mg/24Mg biases up to 85.8‰ and 0.95‰, respectively. The isotopic compositions of Li, Mg, and S separated from seawater were δ7LiL-SVEC = +30.9‰, δ26MgDSM3 = -0.83 ± 0.10‰, and δ34SVCDT = +19.4 ± 0.6‰; each chromatographic peak was completely recovered, and the results were in good agreement with the published values regardless of whether or not chemical suppressor was used. The purification method enables multi-isotope analysis of a sample using various mass spectrometry techniques, such as multiple-collector inductively coupled plasma and thermal ionization mass spectrometry.

[A CASE OF WELL-DIFFERENTIATED LIPOSARCOMA IN THE RIGHT SCROTUM, DIAGNOSED AFTER LOCAL TUMOR EXCISION].

A 71-year-old male was referred to our hospital with right scrotal swelling. The ultrasonography and magnetic resonance imaging revealed a 6.5 cm mass adjacent to the right testicle. Under the preoperative diagnosis of benign intrascrotal lipoma, local tumor excision through scrotal skin incision was performed. The histopathological examination revealed atypical lipomatous tumor/well-differentiated liposarcoma. With the evidence of malignancy, two-stage surgery was mandatory. Thus, radical orchiectomy with high cord ligation and wide excision of surrounding soft tissue structures through inguinal skin incision was performed. However, there were no tumor cells remaining in the resected samples. Neither adjuvant radiation therapy nor chemotherapy has been performed since contrast computed tomography showed no evidence of metastasis. He is free of disease at 1 year postoperatively.

A novel procedure for the assessment of the antioxidant capacity of food components.

Carbonylation, an oxidative modification of the amino group of arginine and lysine residues caused by reactive oxygen species, has emerged as a new type of oxidative damage. Protein carbonylation has been shown to exert adverse effects on various protein functions. Recently, the role of food components in the attenuation of oxidative stress has been the focus of many studies. Most of these studies focused on the chemical properties of food components. However, it is also important to determine their effects on protein functions via post-translational modifications. In this study, we developed a novel procedure for evaluating the antioxidant capacity of food components. Hydrogen peroxide (H2O2)-induced protein carbonylation in HL-60 cells was quantitatively analyzed by using fluorescent dyes (Cy5-hydrazide dye and IC3-OSu dye), followed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and fluorescence determination. Among a panel of food components tested, quinic acid, kaempferol, saponin, squalene, trigonelline, and mangiferin were shown to be capable of suppressing protein carbonylation in HL-60 cells. Our results demonstrated that this fluorescence labeling/SDS-PAGE procedure allows for the detection of oxidative stress-induced protein carbonylation with high sensitivity and quantitative accuracy. This method should be useful for the screening of new antioxidant food components as well as the analysis of their suppression mechanism.

Identification of the chemical form of sulfur compounds in the Japanese pink coral (Corallium elatius) skeleton using µ-XRF/XAS speciation mapping.

The distributions and chemical forms of sulfur compounds in the skeleton of Japanese pink coral (Corallium elatius) were investigated using X-ray spectroscopic techniques combined with micro-focused soft X-ray radiation. Microscopic X-ray fluorescence/soft X-ray photoabsorption (µ-XRF/XAS) speciation mapping clarified that sulfate is the primary species in the coral skeleton, with minor amounts of organic sulfur, whereas both sulfate and organic sulfur coexist in coenenchyme. Analysis of the post-edge region of the XAS spectra confirmed that sulfate ions in the coral skeleton are mainly in the form of gypsum-like inorganic sulfate substituting for the carbonate ions in the calcite skeleton. The sulfate concentration was negatively correlated with the magnesium concentration and positively correlated with that of phosphorus. Speciation mapping of sulfate in the coral skeleton showed clear fluctuations with sulfate concentrations being higher at dark bands, whereas the small amount of organic sulfur had unclear dark/bright bands. These results suggest that the little organic sulfur that is present is contained in the organic matter embedded in the biocrystal of coral skeleton.

Magnesium K-edge XANES spectroscopy of geological standards.

Magnesium K-edge X-ray absorption near-edge structure (XANES) spectra have been investigated to develop a systematic understanding of a suite of Mg-bearing geological materials such as silicate and carbonate minerals, sediments, rocks and chemical reagents. For the model compounds the Mg XANES was found to vary widely between compounds and to provide a fingerprint for the form of Mg involved in geologic materials. The energy positions and resonance features obtained from these spectra can be used to specify the dominant molecular host site of Mg, thus shedding light on Mg partitioning and isotope fractionation in geologic materials and providing a valuable complement to existing knowledge of Mg geochemistry.

Mg isotope fractionation in biogenic carbonates of deep-sea coral, benthic foraminifera, and hermatypic coral.

High-precision Mg isotope measurements by multiple collector inductively coupled plasma mass spectrometry were applied for determinations of magnesium isotopic fractionation of biogenic calcium carbonates from seawater with a rapid Mg purification technique. The mean δ(26)Mg values of scleractinian corals, giant clam, benthic foraminifera, and calcite deep-sea corals were -0.87‰, -2.57‰, -2.34‰, and -2.43‰, suggesting preferential precipitation of light Mg isotopes to produce carbonate skeleton in biomineralization. Mg isotope fractionation in deep-sea coral, which has high Mg calcite skeleton, showed a clear temperature (T) dependence from 2.5 °C to 19.5 °C: 1,000 × ln(α) = -2.63 (±0.076) + 0.0138 (±0.0051) × T(R(2) = 0.82, p < 0.01). The δ(26)Mg values of large benthic foraminifera, which are also composed of a high-Mg calcite skeleton, can be plotted on the same regression line as that for deep-sea coral. Since the precipitation rates of deep-sea coral and benthic foraminifera are several orders of magnitude different, the results suggest that kinetic isotope fractionation may not be a major controlling factor for high-Mg calcite. The Mg isotope fractionation factors and the slope of temperature dependence from deep-sea corals and benthic foraminifera are similar to that for an inorganically precipitated calcite speleothem. Taking into account element partitioning and the calcification rate of biogenic CaCO(3), the similarity among inorganic minerals, deep-sea corals, and benthic foraminiferas may indicate a strong mineralogical control on Mg isotope fractionation for high-Mg calcite. On the other hand, δ(26)Mg in hermatypic corals composed of aragonite has been comparable with previous data on biogenic aragonite of coral, sclerosponges, and scaphopad, regardless of species differences of samples.

Poor nutrition in prepubertal Japanese children at the end of World War II suppressed bone development.

OBJECTIVE: To assess the extent to which malnutrition in childhood affects bone mineral density (BMD) decades later. METHODS: BMDs were compared in healthy women (35-59 years old) who visited our hospital for annual examinations between 1992 and 1993 (group 1) and between 1999 and 2002 (group 2). RESULTS: The BMDs of 50- to 54-year-old women in group 1 averaged 0.86+/-0.15 g/cm2, which was significantly (p<0.001) lower than age-matched women in group 2 (1.02+/-0.16 g/cm2). CONCLUSION: At the end of World War II (1945) undernutrition was rampant throughout Japan, and there were unprecedented numbers of cases of malnutrition. BMD was lower in women who experienced those conditions while they were 5 years old in average, a time when rapid skeletal growth was beginning. Thus, nutrition in childhood is a particularly crucial determinant of lifelong bone health.

[Successful treatment of endometrial carcinoma associated with lung metastasis by paclitaxel and carboplatin chemotherapy].

BACKGROUND: Prognosis of patients with advanced endometrial cancer accompanied by distant metastases is poor. Moreover, there is no established therapy for this cancer. CASE: We treated a 32-year-old woman with endometrial cancer with multiple lung metastases (pT4N0M1). In August 2001, this patient presented with a complaint of abnormal genital bleeding. Endometrial cytology and histology revealed endometrial carcinoma, and chest XP and CT scan detected multiple lung metastases. MRI indicated invasion to the uterine cervix. Therefore, radical hysterectomy with pelvic lymph node dissection was performed. Postoperatively, this patient underwent TJ chemotherapy (paclitaxel 300 mg/body over 3 h, carboplatin 600 mg/body, area under the curve (AUC 5). A total of 9 courses of the regimen were given. Multiple lung shadows on chest XP and computed tomography (CT) were reduced in number and size after 2 courses of TJ chemotherapy. The multiple lung metastases either disappeared or remained as scars after 6 courses. There has been no evidence of recurrence for 20 months after the chemotherapy. CONCLUSION: TJ chemotherapy is considered effective as a postoperative chemotherapy in patients with endometrial cancer with multiple lung metastases.

Genetic and environmental contributions to severe preeclampsia: lack of association with the endothelial nitric oxide synthase Glu298Asp variant in a developing country.

OBJECTIVE: We recently identified a missense variant (Glu298Asp) within exon 7 of the endothelial nitric oxide synthase (eNOS) gene that is associated with severe preeclampsia in the Japanese population. Our objective was to analyze the association between the Glu298Asp eNOS gene variant and severe preeclampsia in a developing country where the incidence of preeclampsia is more frequent. METHODS: The study included 112 Bangladeshi women exhibiting severe preeclampsia and 119 control subjects. Screening for the Glu298Asp eNOS gene variant was carried out by analysis of the polymerase chain reaction-restriction fragment length polymorphism. RESULTS: The analysis revealed that the frequencies of the Glu298Asp variant (Glu298Asp homozygotes and heterozygotes) in the preeclampsia (n = 40; 35%) and control (n = 42; 35%) groups were not significantly (p > 0.05) different. CONCLUSIONS: We conclude that the presence of the Glu298Asp eNOS gene is not a marker for the increased risk of preeclampsia in a population where the level of prenatal care is such that preeclampsia is still frequently seen.

Asymmetric dimethylarginine, an endogenous inhibitor of nitric oxide synthase, in maternal and fetal circulation.

Pronounced dilation of the maternal vasculature occurs during normal pregnancy. Likewise, low resistance characterizes the fetoplacental circulation. Nitric oxide released by endothelial cells is a potent vasodilator known to be a key modulator of both maternal and fetal vascular tone. However, the mechanisms underlying the maternal circulatory adaptations and the low resistance of the fetal circulation remain unknown. The aim of the present study was to compare levels of asymmetric dimethylarginine (ADMA), an endogenous inhibitor of nitric oxide synthase, in the maternal and fetal circulations. High performance liquid chromatography was used to measure asymmetric ADMA in the maternal and umbilical venous plasma. Plasma ADMA levels during the first trimester were 0.29 +/- 0.05, the third trimester before term 0.29 +/- 0.05, and at term 0.32 +/- 0.05 nmol/mL, which were significantly (P <.05) lower than the levels measured in nonpregnant women (0.41 +/- 0.06 nmol/mL). By contrast, ADMA levels in umbilical venous plasma averaged 1.02 +/- 0.18 nmol/mL, significantly (P <.005) higher than maternal levels. Unlike ADMA, levels of plasma L-arginine, the nitric oxide precursor, did not significantly differ among nonpregnant and pregnant women and the fetus.During pregnancy, maternal hemodynamics are modulated, at least in part, by a reduction in ADMA. Conversely, the low resistance to umbilical blood flow is maintained despite substantially higher fetal ADMA levels. Thus, the predominant mechanisms regulating the maternal and fetal circulation apparently differ.

Unilateral ovarian abscess caused by Salmonella.

BACKGROUND: Patients with unilateral ovarian abscesses due to Salmonella are rare. CASE REPORT: A 48-year-old woman with a left ovarian abscess caused by Salmonella group 07 is reported. CONCLUSION: In our patient, the ovary may have been seeded hematogenously by salmonellae and may have evolved into a local infection.

Tubo-ovarian abscess occurring 16 years after supracervical hysterectomy.

BACKGROUND: Supracervical hysterectomy is seldom performed and there are few reports of tubo-ovarian abscess (TOA) after supracervical hysterectomy. CASE: The case of a 49-year-old woman with a right TOA is reported. This patient had received a supracervical hysterectomy 16 years earlier due to rupture of the uterus. At this admission, she presented with complaints of, lower abdominal pain and fever. Bimanual and transvaginal ultrasound examinations demonstrated a tender mass in the right adnexal region. Laparotomy, pathologic examination and microbiologic study confirmed the diagnosis of right TOA. CONCLUSION: After supracervical hysterectomy, patients may develop endocervicitis, parametritis and/or TOA. This series may be a subtype of ascending infections in the female genital tract.