Approaches to Cyclopropa-Fused Quinones. The Synthesis and Photolysis of Some 4,9-Disubstituted 3,3-Dimethyl-3H-benz[f]indazoles

2003 ◽  
Vol 56 (9) ◽  
pp. 903 ◽  
Author(s):  
Gavin E. Collis ◽  
Dieter Wege

Addition of 2-diazopropane to 1,4-naphthoquinone at low temperature, followed by in situ enolization and acetylation or silylation gave 3,3-dimethyl-1H-benz[f]indazol-4,9-diyl diacetate and 3,3-dimethyl-9-(t-butyl-dimethylsilyloxy)-1H-benz[f]indazol-4-ol, respectively. Functional group manipulation of the latter compound provided a number of other 4,9-disubstituted 3,3-dimethyl-3H-benz[f]indazoles. Irradiation of the diacetate led to clean extrusion of nitrogen to give the naphtho[b]cycloproparene and an alkene. Attempts to elaborate the cycloproparene into the derived cyclopropanaphthoquinone were unsuccessful. Of the other 4,9-disubstituted 3,3-dimethyl-3H-benz[f]indazoles examined, only the compound possessing an acetoxy group at C9 was photoactive, and afforded the expected cycloproparene and alkene. Compounds bearing a hydroxy or alkoxy group at C9 were photochemically inert.

1991 ◽  
Vol 57 (3) ◽  
pp. 235-243 ◽  
Author(s):  
Claude Bazin ◽  
Françoise Lemeunier ◽  
Georges Periquet ◽  
Joël Silber

SummaryWe describe herein, a new unstable mutant of the vestigial locus, isolated from a French natural population. From this mutant vestigialalmost (vgal) wild-type flies (vgal+) and extreme vg phenotypes (vge) arose spontaneously without genomic shock. The occurrence of vgal+ or vge alleles depends mostly on the breeding temperature; vgal+ revertants arose principally at low temperature (21 °C) and vge at 28 °C. These events occur mainly in the male germ line and the phenomenon appears to be premeiotic. Our results with in situ hybridization experiments and Southern blots show that the vgal mutation is due to a 2 kb DNA insertion, which is a deleted hobo element. Genetic and molecular analyses show that two distinct events may underly the wild-type revertants. One is the excision of the resident hobo element, the other a further deletion (about 300 bp in the example characterized herein). The vge mutation is probably due to a deletion of vestigial sequences flanking the hobo insertion.


CrystEngComm ◽  
2014 ◽  
Vol 16 (32) ◽  
pp. 7397-7400 ◽  
Author(s):  
Joe Ridout ◽  
Michael R. Probert

Single-crystal X-ray diffraction has been used to elucidate the structure of two polymorphs of isopropyl alcohol, one grown through in situ cryo-crystallisation, the other through high-pressure crystallisation.


1983 ◽  
Vol 96 (6) ◽  
pp. 1677-1689 ◽  
Author(s):  
E Vasile ◽  
M Simionescu ◽  
N Simionescu

We investigated the interaction and transport of low-density lipoprotein (LDL) through the arterial endothelium in rat aorta and coronary artery, by perfusing in situ native, untagged human, and rat LDL. The latter was rendered electron-opaque after it interacted with the endothelial cell and was subsequently fixed within tissue. We achieved LDL electron-opacity by an improved fixation procedure using 3,3'-diaminobenzidine, and mordanting with tannic acid. The unequivocal identification of LDL was implemented by reacting immunocytochemically the perfused LDL with anti LDL-horseradish peroxidase conjugate. Results indicate that LDL is taken up and internalized through two parallel compartmented routes. (a) A relatively small amount of LDL is taken up by endocytosis via: (i) a receptor-mediated process (adsorptive endocytosis) that involved coated pits/vesicles, and endosomes, and, probably, (ii) a receptor-independent process (fluid endocytosis) carried out by a fraction of plasmalemmal vesicles. Both mechanisms bringing LDL to lysosomes supply cholesterol to the endothelial cell itself. (b) Most circulating LDL is transported across the endothelial cell by transcytosis via plasmalemmal vesicles which deliver LDL to the other cells of the vessel wall. Endocytosis is not enhanced by increasing LDL concentration, but the receptor-mediated internalization decreases at low temperature. Transcytosis is less modified by low temperature but is remarkably augmented at high concentration of LDL. While the endocytosis of homologous (rat) LDL is markedly more pronounced than that of heterologous (human) LDL, both types of LDL are similarly transported by transcytosis. These results indicate that the arterial endothelium possesses a dual mechanism for handling circulating LDL: by a high affinity process, endocytosis secures the endothelial cells' need for cholesterol; by a low-affinity nonsaturable uptake process, transcytosis supplies cholesterol to the other cells of the vascular wall, and can monitor an excessive accumulation of plasma LDL. Since in most of our experiments we used LDL concentrations above those found in normal rats, we presume that at low LDL concentrations saturable high-affinity uptake would be enhanced in relation to nonsaturable pathways.


Author(s):  
F. H. Louchet ◽  
L. P. Kubin

Experiments have been carried out on the 3 MeV electron microscope in Toulouse. The low temperature straining holder has been previously described Images given by an image intensifier are recorded on magnetic tape.The microtensile niobium samples are cut in a plane with the two operative slip directions [111] and lying in the foil plane. The tensile axis is near [011].Our results concern:- The transition temperature of niobium near 220 K: at this temperature and below an increasing difference appears between the mobilities of the screw and edge portions of dislocations loops. Source operation and interactions between screw dislocations of different slip system have been recorded.


Author(s):  
J. I. Bennetch

In a recent study of the superplastic forming (SPF) behavior of certain Al-Li-X alloys, the relative misorientation between adjacent (sub)grains proved to be an important parameter. It is well established that the most accurate way to determine misorientation across boundaries is by Kikuchi line analysis. However, the SPF study required the characterization of a large number of (sub)grains in each sample to be statistically meaningful, a very time-consuming task even for comparatively rapid Kikuchi analytical techniques.In order to circumvent this problem, an alternate, even more rapid in-situ Kikuchi technique was devised, eliminating the need for the developing of negatives and any subsequent measurements on photographic plates. All that is required is a double tilt low backlash goniometer capable of tilting ± 45° in one axis and ± 30° in the other axis. The procedure is as follows. While viewing the microscope screen, one merely tilts the specimen until a standard recognizable reference Kikuchi pattern is centered, making sure, at the same time, that the focused electron beam remains on the (sub)grain in question.


Author(s):  
D. A. Smith

The nucleation and growth processes which lead to the formation of a thin film are particularly amenable to investigation by transmission electron microscopy either in situ or subsequent to deposition. In situ studies have enabled the observation of island nucleation and growth, together with addition of atoms to surface steps. This paper is concerned with post-deposition crystallization of amorphous alloys. It will be argued that the processes occurring during low temperature deposition of one component systems are related but the evidence is mainly indirect. Amorphous films result when the deposition conditions such as low temperature or the presence of impurities (intentional or unintentional) preclude the atomic mobility necessary for crystallization. Representative examples of this behavior are CVD silicon grown below about 670°C, metalloids, such as antimony deposited at room temperature, binary alloys or compounds such as Cu-Ag or Cr O2, respectively. Elemental metals are not stable in the amorphous state.


Catalysts ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 618
Author(s):  
Huan Du ◽  
Zhitao Han ◽  
Xitian Wu ◽  
Chenglong Li ◽  
Yu Gao ◽  
...  

Er-modified FeMn/TiO2 catalysts were prepared through the wet impregnation method, and their NH3-SCR activities were tested. The results showed that Er modification could obviously promote SO2 resistance of FeMn/TiO2 catalysts at a low temperature. The promoting effect and mechanism were explored in detail using various techniques, such as BET, XRD, H2-TPR, XPS, TG, and in-situ DRIFTS. The characterization results indicated that Er modification on FeMn/TiO2 catalysts could increase the Mn4+ concentration and surface chemisorbed labile oxygen ratio, which was favorable for NO oxidation to NO2, further accelerating low-temperature SCR activity through the “fast SCR” reaction. As fast SCR reaction could accelerate the consumption of adsorbed NH3 species, it would benefit to restrain the competitive adsorption of SO2 and limit the reaction between adsorbed SO2 and NH3 species. XPS results indicated that ammonium sulfates and Mn sulfates formed were found on Er-modified FeMn/TiO2 catalyst surface seemed much less than those on FeMn/TiO2 catalyst surface, suggested that Er modification was helpful for reducing the generation or deposition of sulfate salts on the catalyst surface. According to in-situ DRIFTS the results of, the presence of SO2 in feeding gas imposed a stronger impact on the NO adsorption than NH3 adsorption on Lewis acid sites of Er-modified FeMn/TiO2 catalysts, gradually making NH3-SCR reaction to proceed in E–R mechanism rather than L–H mechanism. DRIFTS.


2021 ◽  
Vol 13 (8) ◽  
pp. 4591
Author(s):  
Shuanglei Huang ◽  
Daishe Wu

The tremendous input of ammonium and rare earth element (REE) ions released by the enormous consumption of (NH4)2SO4 in in situ leaching for ion-adsorption RE mining caused serious ground and surface water contamination. Anaerobic ammonium oxidation (anammox) was a sustainable in situ technology that can reduce this nitrogen pollution. In this research, in situ, semi in situ, and ex situ method of inoculation that included low-concentration (0.02 mg·L−1) and high-concentration (0.10 mg·L−1) lanthanum (La)(III) were adopted to explore effective start-up strategies for starting up anammox reactors seeded with activated sludge and anammox sludge. The reactors were refrigerated for 30 days at 4 °C to investigate the effects of La(III) during a period of low-temperature. The results showed that the in situ and semi in situ enrichment strategies with the addition of La(III) at a low-concentration La(III) addition (0.02 mg·L−1) reduced the length of time required to reactivate the sludge until it reached a state of stable anammox activity and high nitrogen removal efficiency by 60–71 days. The addition of La(III) promoted the formation of sludge floc with a compact structure that enabled it to resist the adverse effects of low temperature and so to maintain a high abundance of AnAOB and microbacterial community diversity of sludge during refrigeration period. The addition of La(III) at a high concentration caused the cellular percentage of AnAOB to decrease from 54.60 ± 6.19% to 17.35 ± 6.69% during the enrichment and reduced nitrogen removal efficiency to an unrecoverable level to post-refrigeration.


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