Raman spectroscopic study of the hydroxy-phosphate mineral plumbogummite PbAl3(PO4)2(OH,H2O)6

Plumbogummite PbAl3(PO4)2(OH,H2O)6 is a mineral of environmental significance and is a member of the alunite-jarosite supergroup. The molecular structure of the mineral has been investigated by Raman spectroscopy. The spectra of different plumbogummite specimens differ although there are many common features. The Raman spectra prove the spectral profile consisting of overlapping bands and shoulders. Raman bands and shoulders observed at 971, 980, 1002 and 1023 cm−1 (China sample) and 913, 981, 996 and 1026 cm−1 (Czech sample) are assigned to the ν1 symmetric stretching modes of the (PO4)3−, at 1002 and 1023 cm−1 (China) and 996 and 1026 cm−1 to the ν1 symmetric stretching vibrations of the (O3POH)2− units, and those at 1057, 1106 and 1182 (China) and at 1102, 1104 and 1179 cm−1 (Czech) to the ν3 (PO4)3− and ν3 (PO3) antisymmetric stretching vibrations. Raman bands and shoulders at 634, 613 and 579 cm−1 (China) and 611 and 596 cm−1 (Czech) are attributed to the ν4 (δ) (PO4)3− bending vibrations and those at 507, 494 and 464 cm−1 (China) and 505 and 464 cm−1 (Czech) to the ν2 (δ) (PO4)3− bending vibrations. The Raman spectrum of the OH stretching region is complex. Raman bands and shoulders are identified at 2824, 3121, 3249, 3372, 3479 and 3602 cm−1 for plumbogummite from China, and at 3077, 3227, 3362, 3480, 3518 and 3601 cm−1 for the Czech Republic sample. These bands are assigned to the ν OH stretching modes of water molecules and hydrogen ions. Approximate O–H⋯O hydrogen bond lengths inferred from the Raman spectra vary in the range >3.2–2.62 Å (China) and >3.2–2.67 Å (Czech). The minority presence of some carbonate ions in the plumbogummite (China sample) is connected with distinctive intensity increasing of the Raman band at 1106 cm−1, in which may participate the ν1 (CO3)2− symmetric stretching vibration overlapped with phosphate stretching vibrations.

A vibrational spectroscopic study of the phosphate mineral zanazziite - Ca2(MgFe2+)(MgFe2+Al)4Be4(PO4)6⋅6(H2O)

Zanazziite is the magnesium member of a complex beryllium calcium phosphate mineral group named roscherite. The studied samples were collected from the Ponte do Piauí mine, located in Itinga, Minas Gerais. The mineral was studied by electron microprobe, Raman and infrared spectroscopy. The chemical formula can be expressed as Ca2.00(Mg3.15,Fe0.78,Mn0.16,Zn0.01,Al0.26,Ca0.14)Be4.00(PO4)6.09(OH)4.00⋅5.69(H2O) and shows an intermediate member of the zanazziite–greinfeinstenite series, with predominance of zanazziite member. The molecular structure of the mineral zanazziite has been determined using a combination of Raman and infrared spectroscopy. A very intense Raman band at 970 cm−1 is assigned to the phosphate symmetric stretching mode whilst the Raman bands at 1007, 1047, 1064 and 1096 cm−1 are attributed to the phosphate antisymmetric stretching mode. The infrared spectrum is broad and the antisymmetric stretching bands are prominent. Raman bands at 559, 568, 589 cm−1 are assigned to the ν4 out of plane bending modes of the PO4 and HPO4 units. The observation of multiple bands supports the concept that the symmetry of the phosphate unit in the zanazziite structure is reduced in symmetry. Raman bands at 3437 and 3447 cm−1 are attributed to the OH stretching vibrations; Raman bands at 3098 and 3256 are attributed to water stretching vibrations. The width and complexity of the infrared spectral profile in contrast to the well resolved Raman spectra, proves that the pegmatitic phosphates are better studied with Raman spectroscopy.

2-(4-Aminobenzenesulfonamido)-4,6-dimetylpyrimidin-1-ium 2-carboxy-4,6-dinitrophenolate

In the structure of the of the phenolate salt of the sulfa drug sulfamethazine with 3,5-dinitrosalicylic acid, C12H15N4O2S+ C7H3N2O7-, the dihedral angle between the pyrimidine and phenyl rings of the cation is 59.70(17)\%. Cation--anion hydrogen-bonding interactions involving pyrimidine N+-H...O(carboxyl) and amine N-H...O(carboxyl) pairs give a cyclic R2/2(8) motif while secondary N-H...O hydrogen bonds between the aniline group and both sulfone and nitro O-atom acceptors give a two-dimensional structure extending along (001).

A Raman spectroscopic study of the basic carbonate mineral callaghanite Cu2Mg2(CO3)(OH)6⋅2H2O

Raman spectrum of callaghanite, Cu2Mg2(CO3)(OH)6⋅2H2O, was studied and compared with published Raman spectra of azurite, malachite and hydromagnesite. Stretching and bending vibrations of carbonate and hydroxyl units and water molecules were tentatively assigned. Approximate O–H…O hydrogen bond lengths were inferred from the spectra. Because of the high content of hydroxyl ions in the crystal structure in comparison with low content of carbonate units, callaghanite should be better classified as a carbonatohydroxide than a hydroxycarbonate.

Effects of chronic intra-amniotic Ureaplasma parvum (serovar 3 and 6) colonization in the ovine fetus

Background: We have developed a sheep model of intrauterine ureaplasma infection. We aimed to examine the capability of ureaplasmas in the amniotic fluid to infect the fetus and alter fetal development...

Proton-transfer compounds with 4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide (sulfamethazine): the structures and hydrogen-bonding in the salts with 5-nitrosalicylic acid and picric acid

The structures of the anhydrous proton-transfer compounds of the sulfa drug sulfamethazine with 5-nitrosalicylic acid and picric acid, namely 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2-hydroxy-5-nitrobenzoate, C12H15N4O2S(+)·C7H4NO4(-), (I), and 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2,4,6-trinitrophenolate, C12H15N4O2S(+)·C6H2N3O7(-), (II), respectively, have been determined. In the asymmetric unit of (I), there are two independent but conformationally similar cation-anion heterodimer pairs which are formed through duplex intermolecular N(+)-H...Ocarboxylate and N-H...Ocarboxylate hydrogen-bond pairs, giving a cyclic motif [graph set R2(2)(8)]. These heterodimers form separate and different non-associated substructures through aniline N-H...O hydrogen bonds, one one-dimensional, involving carboxylate O-atom acceptors, the other two-dimensional, involving both carboxylate and hydroxy O-atom acceptors. The overall two-dimensional structure is stabilized by π-π interactions between the pyrimidinium ring and the 5-nitrosalicylate ring in both heterodimers [minimum ring-centroid separation = 3.4580 (8) Å]. For picrate (II), the cation-anion interaction involves a slightly asymmetric chelating N-H...O R2(1)(6) hydrogen-bonding association with the phenolate O atom, together with peripheral conjoint R1(2)(6) interactions between the same N-H groups and O atoms of the ortho-related nitro groups. An inter-unit amine N-H...Osulfone hydrogen bond gives one-dimensional chains which extend along a and inter-associate through π-π interactions between the pyrimidinium rings [centroid-centroid separation = 3.4752 (9) Å]. The two structures reported here now bring to a total of four the crystallographically characterized examples of proton-transfer salts of sulfamethazine with strong organic acids.

Simultaneous determination of 6,7-dimethylesculetin and geniposide in rat plasma and its application to pharmacokinetic studies of Yin Chen Hao Tang preparation

A method for the rapid and simultaneous determination of 6,7-dimethylesculetin (CAS 120-08-1) and geniposide (CAS 24512-63-8) in rat plasma has been developed, using validated high performance liquid chromatography (HPLC) with solid phase extraction (SPE). The HPLC analysis was performed on a commercially available column (200 mm x 4.6 mm, 5 microm) with acetonitrile-methanol-0.1% aqueous formic acid as mobile phase and the UV detection at 343 nm and 238 nm for 6,7-dimethylesculetin and geniposide, respectively. The calibration curves for 6,7-dimethylesculetin and geniposide were linear over the range 0.4-25.6 microg/mL and 1.12-71.68 microg/mL, respectively. The lower limits of quantitation were 0.40 microg/ mL and 1.12 microg/mL, and the lower limits of detection were 0.06 microg/mL and 0.09 microg/ mL, respectively. The intra-day and inter-day precision for 6,7-dimethylesculetin and geniposide were < 5%, whereas the absolute recovery percentages were > 74%. A successful application of the developed HPLC analysis was demonstrated for the pharmacokinetic study of a Traditional Chinese Medicine formula of Yin Chen Hao Tang preparation.

Vibrational spectroscopy of the borate mineral pinnoite MgB2O(OH)6

There is a large number of boron containing minerals with water and/or hydroxyl units of which pinnoite MgB2O(OH)6 is one. Some discussion about the molecular structure of pinnoite exists in the literature. Whether water is involved in the structure is ill-determined. The molecular structure of pinnoite has been assessed by the combination of Raman and infrared spectroscopy. The Raman spectrum is characterized by an intense band at 900 cm−1 assigned to the BO stretching vibrational mode. A series of bands in the 1000–1320 cm−1 spectral range are attributed to BO antisymmetric stretching modes and in-plane bending modes. The infrared spectrum shows complexity in this spectral range. Multiple Raman OH stretching vibrations are found at 3179, 3399, 3554 and 3579 cm−1. The infrared spectrum shows a series of overlapping bands with bands identified at 3123, 3202, 3299, 3414, 3513 and 3594 cm−1. By using a Libowitzky type function, hydrogen bond distances were calculated. Two types of hydrogen bonds were identified based upon the hydrogen bond distance. It is important to understand the structure of pinnoite in order to form nanomaterials based upon the pinnoite structure.

Vibrational spectroscopic study of the uranyl selenite mineral derriksite Cu4UO2(SeO3)2(OH)6⋅H2O

Raman spectrum of the mineral derriksite Cu4UO2(SeO3)2(OH)6⋅H2O was studied and complemented by the infrared spectrum of this mineral. Both spectra were interpreted and partly compared with the spectra of demesmaekerite, marthozite, larisaite, haynesite and piretite. Observed Raman and infrared bands were attributed to the (UO2)2+, (SeO3)2−, (OH)− and H2O vibrations. The presence of symmetrically distinct hydrogen bonded molecule of water of crystallization and hydrogen bonded symmetrically distinct hydroxyl ions was inferred from the spectra in the derriksite unit cell. Approximate U–O bond lengths in uranyl and O–H⋯O hydrogen bond lengths were calculated from the Raman and infrared spectra of derriksite.

Electrochemical formation of porous copper 7, 7, 8, 8-tetracyanoquinodimethane and copper 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyanoquinodimethane honeycomb surfaces with superhydrophobic properties

The electrochemical formation of highly porous CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and CuTCNQF4 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) materials was undertaken via the spontaneous redox reaction between a porous copper template, created using a hydrogen bubbling template technique, and an acetonitrile solution containing TCNQ or TCNQF4. It was found that activation of the surface via vigorous hydrogen evolution that occurs during porous copper deposition and TCNQ mass transport being hindered through the porous network of the copper template influenced the growth of CuTCNQ and CuTCNQF4. This approach resulted in the fabrication of a honeycomb layered type structure where the internal walls consist of very fine crystalline needles or spikes. This combination of microscopic and nanoscopic roughness was found to be extremely beneficial for anti-wetting properties where superhydrophobic materials with contact angles as high as 177° were created. Given that CuTCNQ and CuTCNQF4 have shown potential as molecular based electronic materials in the area of switching and field emission, the creation of a surface that is moisture resistant may be of applied interest.

Actigraphy assessment of mother's sleep at 6, 12 & 18 weeks postpartum

Introduction: Mothers’ sleep during the postpartum period is commonly characterised by bouts of sleep across the night, resulting in low sleep efficiency and daytime sleepiness. Understanding of the nature of mothers’ sleep disruption needs to incorporate indices of both sleep quantity and sleep quality, but objective assessment of sleep disturbance experienced during the first postpartum months has not been investigated in great detail. This longitudinal study aimed to objectively measure mothers’ sleep during the first 18 weeks postpartum, to ascertain the level of sleep disturbance experienced. Method: Eleven mothers (Mean age = 29.82, SD = 4.45) from Australia wore Actiwatch-2 devices for up to 7 days and nights at 6, 12 and 18 weeks postpartum. For each night of recording, a number of sleep bouts were identified. Total sleep time (TST) was calculated as the total number of minutes across the night within these bouts. Sleep efficiency was calculated as the percentage of minutes across the night classified as being part of a sleep bout, with higher scores indicating higher efficiency. Sleep quality captured the efficiency of sleep within sleep bouts, and was calculated as the percentage of epochs classified as sleep within sleep bouts, with higher scores indicating higher sleep quality. Results: At 6 weeks postpartum, mean total sleep time was 420.22 minutes (SD = 50.61). Total sleep time did not significantly differ across the assessment; however there was a trend towards an increase over time. Sleep efficiency increased across the time periods (F(2,10) = 10.30, p = .001), with a significant increase between week 12 and week 18. At 6 weeks postpartum, mean sleep quality was 93.15% (SD = 2.68) and scores did not significantly change across the assessment periods. While there was no relationship between sleep efficiency and sleep quality during weeks 6 and 12, a significant positive relationship was observed at week 18, r2 = .52, p = .013. Conclusions: Within this sample, a low level of disruption was consistently shown within the mothers’ night time sleep bouts. However, overall sleep efficiency suggested a significant proportion of time spent awake between sleep bouts. While TST remained stable over time, overall sleep efficiency improved, suggesting the mothers’ sleep was becoming more consolidated. A single sleep bout a night was not often experienced.

Prevalence of childhood sexual abuse among 2508 college students in 6 provinces of China [中国6省市2508名大学生儿童期性虐待经历回顾性调查]

OBJECTIVE To assess the prevalence of childhood sexual abuse (CSA) in college students and to explore the association of CSA with youth mental health problem. METHODS A retrospective survey was conducted among 2508 students (females 1360, males 1148) in Nov. 2003 to Mar. 2004. The students were from 6 colleges/universities in Beijing, Hebei, Shanxi, Jiangsu, Shaanxi and Anhui provinces of China. RESULTS Of the 2508 students, 24.8% of females and 17.6% of males reported one or more types of nonphysical contact CSA (females 20.0% vs. males 14.6%) or/and physical contact CSA (females 14.1% vs. males 7.8%) before the age of 16 years. Risk of any CSA was not associated with the existence of siblings (one-child vs. two-or more child families), rural/non-rural residence during childhood, or parental education. Compared with their peers who had no CSA, the students with CSA showed significantly higher mean scores of psychological symptoms of somatization, obsessiveness, interpersonal sensitivity, depression, anxiety, hostility, phobic anxiety, paranoid ideation and psychoticism. CONCLUSION The problem of CSA was not uncommon and there was a significant correlation between CSA experience and students mental health problems. More attention should be paid on CSA prevention and provision of health services for the victims.

Secretome and degradome profiling shows that Kallikrein-related peptidases 4, 5, 6, and 7 induce TGFβ-1 signaling in ovarian cancer cells

Kallikrein-related peptidases, in particular KLK4, 5, 6 and 7 (4-7), often have elevated expression levels in ovarian cancer. In OV-MZ-6 ovarian cancer cells, combined expression of KLK4-7 reduces cell adhesion and increases cell invasion and resistance to paclitaxel. The present work investigates how KLK4-7 shape the secreted proteome ("secretome") and proteolytic profile ("degradome") of ovarian cancer cells. The secretome comparison consistently identified >900 proteins in three replicate analyses. Expression of KLK4-7 predominantly affected the abundance of proteins involved in cell-cell communication. Among others, this includes increased levels of transforming growth factor β-1 (TGFβ-1). KLK4-7 co-transfected OV-MZ-6 cells share prominent features of elevated TGFβ-1 signaling, including increased abundance of neural cell adhesion molecule L1 (L1CAM). Augmented levels of TGFβ-1 and L1CAM upon expression of KLK4-7 were corroborated in vivo by an ovarian cancer xenograft model. The degradomic analysis showed that KLK4-7 expression mostly affected cleavage sites C-terminal to arginine, corresponding to the preference of kallikreins 4, 5 and 6. Putative kallikrein substrates include chemokines, such as growth differentiation factor 15 (GDF 15) and macrophage migration inhibitory factor (MIF). Proteolytic maturation of TGFβ-1 was also elevated. KLK4-7 have a pronounced, yet non-degrading impact on the secreted proteome, with a strong association between these proteases and TGFβ-1 signaling in tumor biology. © 2013 Federation of European Biochemical Societies.