Metabolic profiling of normal and hypertensive rat kidney tissues by hrMAS-NMR spectroscopy

Intact kidney tissue samples of normal and spontaneously hypertensive rats (SHRs) were analyzed by hrMAS-NMR spectroscopy and principal component analysis (PCA). Radial components (cortex, outer stripe of the outer medulla, inner stripe of the outer medulla, and papilla) were sampled from various regions across the kidney from multiple animals in order to establish inter- and intra-animal variability. The effects of temperature were also measured. Papilla was differentiated from the other tissue types, and this variation by tissue type was greater than the effect of temperature on the samples (spectra were compared from samples at 2 and 30 °C). This study also revealed long term stability issues of tissue storage at -80 °C. The PCA showed that the greatest differentiation between normal rats and SHRs was found in the cortex and the regions in the NMR spectra that were correlated with this variation were identified.Abbreviations hrMAS High-resolution magic angle spinning - NMR Nuclear magnetic resonance - PCA Principal component analysis - CSA Chemical shift anisotropy - DD Dipolar coupling - SHR Spontaneously hypertensive rat     

Polymerization and characterization of nitrile-terminated diacetylene materials

A family of nitrile-terminated diacetylene materials were synthesized. Samples were prepared in various forms and polymerization was performed photochemically and thermally. The resulting materials exhibited low molecular weights and were obtained in low yields. Although the diacetylene group had oligomerized, no evidence was found in support of ? C?N? chain formation. Thermochromism was exhibited by the irradiated 8-nitrile sample and a molecular interpretation of this chromic transition was discussed. Diffraction data implied that strong intermolecular interactions were present between adjacent nitrile groups in the low temperature phase. It is suggested that stresses are built up during polymerization which cause the low degree of polymerization and yield.     

A study of the thermal and light induced spin transition in [FeL2](BF4)2 and [FeL2](ClO4)2 L=2,6-di(3-methylpyrazol-1-yl)pyrazine

The spin crossover compounds [FeL2](BF4)2, L=2,6-di(3-methylpyrazol-1-yl)pyrazine and [FeL2](ClO4)2 have very unusual two stage spin transitions which are initially steep and then become more gradual. A detailed variable temperature single crystal X-ray diffraction study has shown that the course of the spin transition is controlled by an order-disorder transition in the counter anions. The high and low spin states both crystallise in the tetragonal space group I4, the structures of the high and low spin states are presented at 290 and 30 K, respectively. The title compounds are shown to undergo LIESST (Light Induced Excited Spin State Trapping) under irradiation with either red or green laser light with wavelengths of 632.8 and 532.06 nm, respectively, at 30 K. The cell parameters for the tetragonal photo-induced metastable high spin state at this temperature are a= 9.169(6), c= 17.77(1) A for [FeL2](ClO4)2 with an increase in unit cell volume of 21 A3, and a= 9.11(1), c= 17.75(2) A and an increase in volume of 42.8 A3 for [FeL2](BF4)2.     

Aza-analogues of cage compounds: Potential precursors to azacubanes and 1-azahomocubanes

Exploration of the reactions of the 9-azahomocubane system led to derivatives of two small-ring systems containing aza-bridging atoms, 5-azatetracyclo[4.2.0.0^3,8.0^4,7]octane and 9-azatetracyclo[4.3.0.0^2,5.0^4,7]nonane. The structures were characterized by X-ray diffraction analyses. There are no prior X-ray structural reports on these systems.     

Enantiopure fluorous bis(oxazolines): synthesis and applications in catalytic asymmetric reactions

Various enantiopure fluorous bis(oxazolines) with fluorine content between 52.7 and 58.7% have been synthesized by a simple reaction sequence that involved the introduction of two fluorinated ponytails by alkylation of the corresponding nonfluorous bis(oxazolines). These new ligands have been used in palladium-catalyzed alkylation of rac-(E)-1,3-diphenylpropenyl acetate with carbon nucleophiles and in copper-catalyzed oxidation of cycloalkenes; these ligands exhibited enantioselectivities up to 98 and 77%, respectively, quite close to the values obtained using the analogous nonfluorous bis(oxazolines). These ligands could be easily recovered by liquid-liquid extraction or solid-liquid separation and reused with the same enantioselectivities.     

LCAO-MO-SCF-CI semi-empirical π-electron calculations on heteroaromatic systems

The electronic spectra and structure for phenol, the three dihydroxybenzene isomers, and - and -naphthol have been calculated using a modification of the Pariser-Parr-Pople method. Core integrals are defined to be essentially independent of geometry and orthogonalized atomic orbitals are used. The electronic transitions considered involve singlet-singlet and triplet-triplet ^* excitations. A limited configuration interaction has been included, involving either single electron excitations or both single and double electron excitations between the two highest occupied and the two lowest unoccupied molecular orbitals. Agreement between calculated and experimental values is good, and calculated values for oscillator strengths are considerably improved when double electron excitations are admitted.

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Zusammenfassung Die Elektronenspektren und Struktur von Phenol, den drei Isomeren des Dihydroxybenzols und - und -Naphthol wurden mit einer Modifikation der PPP-Methode berechnet. Die Rumpfintegrale werden so definiert, daß sie im wesentlichen unabhängig von der Geometrie sind; es werden orthogonalisierte Atomorbitale benutzt. Die betrachteten Elektronenübergänge enthalten Singulett-Singulett- und Triplett-Triplett- ^*-Übergänge. Es wurde eine begrenzte Konfigurationswechselwirkung eingeschlossen, die nur Einelektronen- oder Ein- und Zweielektronenanregung zwischen den beiden höchsten besetzten und den beiden niedrigsten unbesetzten MO's enthält. Es besteht gute Übereinstimmung von berechneten und experimentellen Daten. Die berechneten Werte für Oszillatorenstärken werden erheblich verbessert, wenn man Zweielektronenanregung einbezieht.

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Résumé Les spectres électroniques et les structures du phénol, des trois dihydroxybenzènes isomères, de l' et du naphtol ont été calculé pour une variante de la méthode de Pariser-Parr-Pople. Les intégrales de coeur sont définies de manière à être indépendantes de la géométrie et des orbitales atomiques orthogonalisées sont employées. On considère les transitions électroniques ^* singulet-singulet et triplet-triplet. Une interaction de configuration limitée a été effectuée en considérant soit des minoexcitations soit des mono et des diexcitations de la plus haute orbitale occupée aux deux orbitales libres les plus basses. L'accord entre les valeurs calculées et les valeurs expérimentales est bon, et les valeurs calculées des forces oscillatrices sont considérablement améliorées lorsque l'on tient compte des états diexcités.

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This investigation was supported by a National Science Foundation grant, No. GB-4065. Abstracted in part from the Ph. D. thesis of G. W. Pukanic, Duquesne University, 1967.     

Solid State NMR and TG/MS Study on the Transformation of Methyl Groups During Pyrolysis of Preceramic Precursors to SiOC Glasses

The sol-gel method was used to prepare two different starting gels containing SiCH₃-groups for the preparation of SiOC ceramics. To understand the role of Si—H bonds in the incorporation of carbon into the SiOC network, gels prepared from a 1:2 mixture of triethoxysilane and methyldiethoxysilane (T^HD^H2) and solely methyltriethoxysilane (T^Me) were investigated. Thermogravimetric analysis coupled with mass spectroscopy (TG-MS) in inert atmosphere was performed to attain an insight into the decomposition reactions involved during gel-glass transformation. Samples calcined at different temperatures up to 1000°C were characterized by ²⁹Si and ¹³C magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The presence of SiH groups in the starting gel allows an efficient conversion of Si—CH₃ groups into CSi₄ sites at lower temperatures. As a result, despite a much lower amount of carbon in the starting T^HD^H2 gel (C/Si = 0.33) compared to the T^Me gel (C/Si = 1), the amount of carbon inserted into the SiOC network of both glasses is equivalent, but the T^Me sample contains the 10 fold amount of free carbon.     

EVENTS SURROUNDING THE EARLY DEVELOPMENT OF EUGLENA CHLOROPLASTS. 12. SPECTROSCOPIC EXAMINATION OF THE PROTOCHLOROPHYLL(IDE) PHOTOTRANSFORMATION IN INTACT CELLS*

Abstract— Absorption measurements in the 600–720 nm region of dark-grown cells of Euglena gracilis Klebs var. bacillaris Cori were made in vivo at room temperature using computer-assisted spectrophotometry. Dark-grown wild-type cells have a prominent absorption maximum at 634 nm due to protochlorophyll(ide) absorption. Upon illumination, the absorption at 634nm decreases and a peak appears at 674nm, representing the phototransformation of protochlorophyll(ide) to chlorophyll(ide). Using difference spectroscopy, the resynthesis in the dark of protochlorophyll(ide) by previously-illuminated wild-type dark-grown cells was found to begin at about 10min after illumination and reached completion by about 25 min, the amount of protochlorophyll(ide) resynthesized being equivalent to that of dark-grown cells. Resynthesis of protochlorophyll(ide) following a second illumination follows the same kinetics, indicating that protochlorophyll(ide) resynthesis is under tight regulation, possibly via feedback control. Cells of dark-grown wild-type and W₃BUL, a mutant lacking protochlorophyll(ide) contain a component absorbing at 658 nm which does not undergo phototransformation when examined by difference spectroscopy at room and liquid N₂ temperatures. Following the phototransformation of protochlorophyll(ide) 634 to chlorophyll(ide) 674, the chlorophyll(ide) 674 shifts to shorter wavelengths, ultimately to 671 nm. Possible relationships among the various spectroscopic forms of protochlorophyll(ide) and chlorophyll(ide) at room temperature and liquid N₂ temperature in Euglena and higher plants are presented. It is concluded that Euglena, unlike older, etiolated higher plants, contains only protochlorophyll(ide) 634, making it an excellent system in which to examine the phototransformation of this pigment species in the absence of other forms.     

Canady Cold Helios Plasma Reduces Soft Tissue Sarcoma Viability by Inhibiting Proliferation,Disrupting Cell Cycle,and Inducing Apoptosis: A Preliminary Report

Soft tissue sarcomas (STS) are a rare and highly heterogeneous group of solid tumors, originating from various types of connective tissue. Complete removal of STS by surgery is challenging due to the anatomical location of the tumor, which results in tumor recurrence. Additionally, current polychemotherapeutic regimens are highly toxic with no rational survival benefit. Cold atmospheric plasma (CAP) is a novel technology that has demonstrated immense cancer therapeutic potential. Canady Cold Helios Plasma (CHCP) is a device that sprays CAP along the surgical margins to eradicate residual cancer cells after tumor resection. This preliminary study was conducted in vitro prior to in vivo testing in a humanitarian compassionate use case study and an FDA-approved phase 1 clinical trial (IDE G190165). In this study, the authors evaluate the efficacy of CHCP across multiple STS cell lines. CHCP treatment reduced the viability of four different STS cell lines (i.e., fibrosarcoma, synovial sarcoma, rhabdomyosarcoma, and liposarcoma) in a dose-dependent manner by inhibiting proliferation, disrupting cell cycle, and inducing apoptosis-like cell death.