Synthesis of 4b,5,10a,11-tetrahydroindeno[1,2-b]quinolin-10-ones from Baylis-Hillman adducts

We developed an efficient synthetic method for indenoquinoline skeletons from Baylis-Hillman adducts. 4b,5,10a,11-Tetrahydroindeno[1,2-b]quinolin-10-ones and 7H-indeno[2,1-c]quinolines were prepared from Baylis-Hillman adducts in polyphosphoric acid.     

A new synthesis of 1,2,3,5‐tetrahydroimidazo[2,3‐b]‐[1,3]benzodiazocines

A new synthesis of 6‐carbomethoxy‐1,2,3,5‐tetrahydroirnidazo[2,3‐b][1,3]benzodiazocines 13 by the intramolecular cycloaddition reaction of methyl 2‐(1‐aziridinylmethyl)‐3‐(2‐ureidophenyl)propenoates 10 under Appel's dehydration conditions is described. The latter were readily obtained from 2‐nitrobenzalde‐hyde with methyl acrylate through the Baylis‐Hillman reaction.     

Hollow fiber membrane-protected solid-phase microextraction of triazine herbicides in bovine milk and sewage sludge samples

A porous polypropylene hollow fiber membrane (HFM)-protected solid-phase microextraction (HFM-SPME) procedure in conjunction with gas chromatography/mass spectrometric analysis for use in the determination of triazine herbicides in bovine milk samples is described. A 65-microm polydimethylsiloxane-divinylbenzne (PDMS-DVB) SPME fiber was protected by an HFM. HFM-SPME experimental parameters such as fiber type, extraction time, extraction temperature and salt concentration were investigated and optimized. The relative standard deviations for the reproducibility of the optimized HFM-SPME method varied from 4.30 to 12.37%. The correlation coefficients of the calibration curves were between 0.9799 and 0.9965 across a concentration range of 0-200 microg l(-1). The method detection limits for triazines in bovine milk were in the range of 0.003-0.013 microg l(-1) and limits of quantification were in the range of 0.006-0.021 microg l(-1). The suitability of HFM-SPME was extended to the analysis of the herbicides in sewage sludge samples. The results demonstrate that HFM-SPME was an efficient pretreatment and enrichment procedure for complex matrices.     

Structural Relationships between the Hemiporphyrazine Macrocyclic Ligand and its Metal Complexes. II.: Planar Neutral Ligand,C26H16N8, and Four Isomorphous Metal Complexes, [M(C26H16N8)(H2O)], M=Mn(II), Co(II), Cu(II), Zn(II)

Crystal and molecular structures of the planar neutral ligand, C₂₆H₁₆N₈, and the four isomorphous five-coordinated metal complexes, [M(C₂₆H₁₆N₈)(H₂O)], M = Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH₂, C₂₆H₁₆N₈, belongs to the P 2₁/c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3) Ä, β=94.66(6)°. The metal complexes monohydrate Mhp-H₂O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8×19.3×23.7 ų. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH₂·H₂O) and the nickel complex [Nihp]⁵. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)Å. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H₂O), M(II)-N1 (imine), M(II)-N3 (pyridine) are: 2.19(1), 2.00(2), 2.27(2)Å respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)Å for the cobalt complex; 2.33(1), 1.92(3), 2.18(1)Å for the copper complex; 2.110(5), 1.964(6), 2.252(6)Å for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.     

14‐Membered Cyclopeptides from Paliurus ramosissimus and P. hemsleyanus

Six 14‐membered cyclopeptide alkaloids, i.e., ramosines A–C, mucronine J, and lotusines A and D, were isolated from the roots of Paliurus ramosissimus, and an additional four, hemsines A–D, from the roots of P. hemsleyanus. Among these, ramosines A–C ( 1, 5 , and 6 , resp.) and hemsines A and B ( 7 and 8 , resp.) are new bases of the amphibine‐B type, and hemsines C and D ( 9 and 10 , resp.) are new integerrine‐type alkaloids. Additionally, ramosine C ( 6 ) represents the first 14‐membered cyclopeptide alkaloid possessing a substitution (? OH) at C(13′). Their structural elucidations were based on spectral analysis and molecular‐modeling studies. Pronounced solvent effects in the ¹H‐ and ¹³C‐NMR spectra of these two types of alkaloids were observed.     

Enhancing the enantioselectivity of lipase in transesterification by substrate matching: an enzyme memory based approach

The substrate matching strategy is described as a new approach for effectively enhancing the lipase enantioselectivity in organic solvent. In the lipase-catalyzed transesterifications of 3a-c, higher enantioselectivities have been achieved using 1a-c, respectively, as the structurally matched acyl donors.     

Potentiometric determination of silver with dithiooxamide

Potentiometric titration with dithiooxamide solution can be used to determine silver in the 0.0100–50.0 p.p.m range with an average accuracy of ca. 0.5% and a relative standard deviation ranging from 1.26% to 0.03% The metals commonly associated with silver can be masked with fluoride and EDTA The advantages of the method over other potentiometric and common spectrophotometric methods are outlined.     

Investigation of the Curing Mechanism in the GPTS/APTS Binder System

The acid catalyzed sol-gel reaction in the mixed binder system, 3-glycidoxypropyltrimethoxysilane (GPTS)/3-aminopropyltriethoxysilane (APTS) was investigated and one step and two step synthesis process were compared. Hydrolysis product was observed using the ¹H, ¹³C NMR and Raman spectra. Especially, based on the Raman spectra, epoxy ring opening was observed, varying the ratio of GPTS to APTS. The two step process made clear sol, while the one step process resulted in a milky suspension. According to the Raman spectra, the epoxy ring opening reaction kinetics proceeded slower in the two step process than one step process. Throughout the two step process, it was possible to apply the binder for the coating of substrate.     

Cholesterol levels and plasma membrane fluidity in 3T3 and SV101-3T3 cells.

Polyene antibiotics such as filipin selectively inhibit wheat germ agglutinin-induced agglutination of transformed and malignant cells compared to normal cells (Hatten ME, Burger MM: Biochemistry 18: 739, 1979). Since filipin binds specifically to cholesterol, we measured cholesterol levels in 3T3 cells and SV101-3T3 cells. SV101-3T3 cells contained 50-100% more cholesterol per cell than 3T3 cells. Both cell types were starved for cholesterol by growth in lipid-depleted medium plus 25-hydroxycholesterol. The cholesterol level of SV101-3T3 cells decreased by 30-50%, while the level in 3T3 cells remained constant. Filipin-stained SV101-3T3 cells revealed bright patches of filipin under fluorescence microscopy. These patches were absent in 3T3 cells and in SV101-3T3 and 3T3 cells starved for cholesterol. We selectively labeled plasma membranes of these cells with a spin label analog of phosphatidylcholine. The spin label indicated differences in plasma membrane fluidity that may be related to the different cholesterol levels in 3T3 and SV101-3T3 cells.     

Flow goes forward and cells step backward: endothelial migration

Systemic and pulmonary circulations constitute a complex organ that serves multiple important biological functions. Consequently, any pathological processing affecting the vasculature can have profound systemic ramifications. Endothelial and smooth muscle are the two principal cell types composing blood vessels. Critically, endothelial proliferation and migration are central to the formation and expansion of the vasculature both during embryonic development and in adult tissues. Endothelial populations are quite heterogeneous and are both vasculature type- and organ-specific. There are profound molecular, functional, and phenotypic differences between arterial, venular and capillary endothelial cells and endothelial cells in different organs. Given this endothelial cell population diversity, it has been challenging to determine the origin of endothelial cells responsible for the angiogenic expansion of the vasculature. Recent technical advances, such as precise cell fate mapping, time-lapse imaging, genome editing, and single-cell RNA sequencing, have shed new light on the role of venous endothelial cells in angiogenesis under both normal and pathological conditions. Emerging data indicate that venous endothelial cells are unique in their ability to serve as the primary source of endothelial cellular mass during both developmental and pathological angiogenesis. Here, we review recent studies that have improved our understanding of angiogenesis and suggest an updated model of this process.Subject terms: Cell lineage, Chemotaxis