Biliverdin Chiral Derivatives as Chiroptical Switches for pH and Metal Cation Sensing

Author(s):  
Simone Ghidinelli ◽  
Sergio Abbate ◽  
Giuseppe Mazzeo ◽  
Stefan E. Boiadjiev ◽  
David A Lightner ◽  
...  

A series of six optically active derivatives of the bile pigment biliverdin, namely (βS,βʹS)-dimethylmesobiliverdin-XIIIα cyclic esters of linear diols [HO(CH2)nOH] where n = 1-6, have been investigated by vibrational circular...

2009 ◽  
Vol 50 (38) ◽  
pp. 5347-5350 ◽  
Author(s):  
Viatcheslav I. Sokolov ◽  
Vasily V. Bashilov ◽  
Fedor M. Dolgushin ◽  
Natalya V. Abramova ◽  
Kyrill K. Babievsky ◽  
...  

1978 ◽  
Vol 9 (27) ◽  
Author(s):  
A. N. KASHIN ◽  
V. A. KHUTORYANSKII ◽  
V. N. BAKUNIN ◽  
I. P. BELETSKAYA ◽  
O. A. REUTOV

1977 ◽  
Vol 8 (16) ◽  
pp. no-no
Author(s):  
D. D. MILLER ◽  
F. L. HSU ◽  
R. R. JUN. RUFFOLO ◽  
P. N. PATIL

2019 ◽  
Vol 213 ◽  
pp. 440-445 ◽  
Author(s):  
Hongfen Chen ◽  
Xiaoping Yang ◽  
Le Bo ◽  
Shiqing Wang ◽  
Dongmei Jiang ◽  
...  

Polymers ◽  
2019 ◽  
Vol 11 (10) ◽  
pp. 1641 ◽  
Author(s):  
Ilya Nifant’ev ◽  
Andrey Shlyakhtin ◽  
Maxim Kosarev ◽  
Dmitry Gavrilov ◽  
Stanislav Karchevsky ◽  
...  

Catalytic ring-opening polymerization (ROP) of cyclic esters (lactides, lactones) and cyclic ethylene phosphates is an effective way to process materials with regulated hydrophilicity and controlled biodegradability. Random copolymers of cyclic monomers of different chemical nature are highly attractive due to their high variability of characteristics. Aryloxy-alkoxy complexes of non-toxic metals such as derivatives of 2,6-di-tert-butyl-4-methylphenoxy magnesium (BHT-Mg) complexes are effective coordination catalysts for homopolymerization of all types of traditional ROP monomers. In the present paper, we report the results of density functional theory (DFT) modeling of BHT-Mg-catalyzed copolymerization for lactone/lactide, lactone/ethylene phosphate and lactide/ethylene phosphate mixtures. ε-Caprolactone (ε-CL), l-lactide (l-LA) and methyl ethylene phosphate (MeOEP) were used as examples of monomers in DFT simulations by the Gaussian-09 program package with the B3PW91/DGTZVP basis set. Both binuclear and mononuclear reaction mechanistic concepts have been applied for the calculations of the reaction profiles. The results of calculations predict the possibility of the formation of random copolymers based on l-LA/MeOEP, and substantial hindrance of copolymerization for ε-CL/l-LA and ε-CL/MeOEP pairs. From the mechanistic point of view, the formation of highly stable five-membered chelate by the products of l-LA ring-opening and high donor properties of phosphates are the key factors that rule the reactions. The results of DFT modeling have been confirmed by copolymerization experiments.


Blood ◽  
1946 ◽  
Vol 1 (2) ◽  
pp. 99-120 ◽  
Author(s):  
CECIL JAMES WATSON

Abstract The transition of hemoglobin to bile pigment, at least under normal conditions, is believed to occur via an intermediate biliverdin-globin-iron (verdohemoglobin) and not over the stages of hematin and protoporphyrin. It is probable that the next step is a reduction to bilirubin with splitting off of iron. There is much reason to believe that the globin remains attached until the bilirubin passes through the liver cell, bilirubinglobin exhibiting a delayed or indirect van den Bergh reaction and not being excreted in the urine; the sodium bilirubinate of the bile exhibiting a prompt (1') van den Bergh reaction and being readily excreted in the urine. The former type is characteristic of retention, the latter of regurgitation jaundice. The appearance of bilirubin in the urine is believed to be related to the concentration in the blood of the 1' or prompt bilirubin, rather than that of the total bilirubin. It is evident that the threshold may be considerably lower at the onset of jaundice, as, for example, in hepatitis, than during its defervescence. This undoubtedly accounts for the appearance of bilirubinuria prior to recognizable jaundice in certain instances, likewise for its presence in the cases of so-called "hepatitis without jaundice." In retention jaundice marked elevation of the total serum bilirubin is unassociated with bilirubinuria; in these cases the increase of bilirubin is mainly of the delayed or indirect reacting type. Further evidence is presented of the essential difference between the 1' or prompt, and the T minus 1', or delayed and indirect reacting bilirubins. This consists of a change of the order of reaction at one minute after adding the diazonium salt. The normal upper limit of the 1' bilirubin has been shown to be in the neighborhood of 0.2. mg. per 100 cc.; figures well below this value are usually obtained. Further experience with the erythrocyte protoporphyrin in the anemias has revealed that this determination, quite apart from its fundamental interest, is at times of diagnostic value. Thus in several instances a significant elevation of the erythrocyte protoporphyrin has indicated that the initial impression of pernicious anemia was incorrect, and has led to the search for other information. Conversely, a low normal value in the presence of anemia has often correctly indicated or confirmed the diagnosis of pernicious anemia. Marked elevations have aided in confirming the presence of iron deficiency and have given some insight into the degree of its severity and chronicity. In certain cases, high values for the erythrocyte protoporphyrin have suggested the possibility of heavy metal toxicity, the existence of which has then been borne out by subsequent study.


Synlett ◽  
2019 ◽  
Vol 30 (06) ◽  
pp. 738-742
Author(s):  
Akira Yanagisawa ◽  
Yoshiki Yamashita ◽  
Chika Uchiyama ◽  
Ryuta Nakano ◽  
Moe Horiguchi ◽  
...  

A catalytic enantioselective α-amination reaction of alkenoate cyclic esters with dialkyl azodicarboxylates was achieved by using a 3,3′-di(1-naphthyl)-substituted (R)-BINOL–dibromostannane complex as a chiral precatalyst in the presence of a sodium alkoxide and an alcohol. Optically active α-hydrazino ketones were obtained in moderate to high yields and with up to 91% ee in the presence of the chiral tin alkoxide generated in situ.


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