Side Reactions with an Equilibrium Constraint: Detailed Mechanism of the Substitution Reaction of Tetraplatin with dGMP as a Starting Step of the Platinum(IV) Reduction Process

2017 ◽  
Vol 121 (17) ◽  
pp. 4400-4413 ◽  
Author(s):  
Filip Šebesta ◽  
Jaroslav V. Burda
Author(s):  
Ali Kh. Salamov ◽  
Abdulakh K. Mikitaev ◽  
Aues A. Beev ◽  
Julietti A. Beeva ◽  
Mukhamed Kh. Ligidov ◽  
...  

The article deals with the study of influence of the synthesis conditions on the molecular weight of polyaryleneetherketones (PAEK), received with nucleophilic substitution reaction of activated aryl halide. The synthesis of PAEK with the nucleophilic substitution reaction carried out as partially hydrolyzed homopolycondensation of phenolates and aromatic dihalides containing a carbonyl group in the molecule and derivatives of polycondensation of aromatic bisphenols with activated aromatic dihalides, and aromatic nitro compounds. The nucleophilic substitution of halogen in aryldihalogens proceeds through formation of Meisenheimer complex, where the negative charge of the electron-electron ring stabilizes the group. The high efficiency of the synthesis of PAEK with nucleophilic substitution reaction is mainly determined with several factors, the main of which are: 1) the structure of the starting monomers; 2) the nature of the solvent; 3) the nature of phenolate; 4) side reactions. For these materials it was revealed that the ratio of nucleophilic and electrophilic reagents has pronounced effect on the molecular weight of the obtained polymer, without affecting the poly dispersion. PAEK synthesis processes are optimized by controlling the replacement of some of the monomers, the temperature and concentration of reactants change. It was shown that the polyarylene ether ketones and copolymers have a high thermal heat resistance, mechanical properties. They show considerable heat resistance in air, capable of forming a transparent film and melts. Thus, data of literature review show that the nucleophilic substitution reaction is promising for PAEK synthesis of various chemical structures and produces polymers having valuable properties.


Author(s):  
James F. Hainfeld ◽  
Frederic R. Furuya

Glutaraldehyde is a useful tissue and molecular fixing reagents. The aldehyde moiety reacts mainly with primary amino groups to form a Schiff's base, which is reversible but reasonably stable at pH 7; a stable covalent bond may be formed by reduction with, e.g., sodium cyanoborohydride (Fig. 1). The bifunctional glutaraldehyde, (CHO-(CH2)3-CHO), successfully stabilizes protein molecules due to generally plentiful amines on their surface; bovine serum albumin has 60; 59 lysines + 1 α-amino. With some enzymes, catalytic activity after fixing is preserved; with respect to antigens, glutaraldehyde treatment can compromise their recognition by antibodies in some cases. Complicating the chemistry somewhat are the reported side reactions, where glutaraldehyde reacts with other amino acid side chains, cysteine, histidine, and tyrosine. It has also been reported that glutaraldehyde can polymerize in aqueous solution. Newer crosslinkers have been found that are more specific for the amino group, such as the N-hydroxysuccinimide esters, and are commonly preferred for forming conjugates. However, most of these linkers hydrolyze in solution, so that the activity is lost over several hours, whereas the aldehyde group is stable in solution, and may have an advantage of overall efficiency.


Author(s):  
C. Vannuffel ◽  
C. Schiller ◽  
J. P. Chevalier

Recently, interest has focused on the epitaxy of GaAs on Si as a promising material for electronic applications, potentially for integration of optoelectronic devices on silicon wafers. The essential problem concerns the 4% misfit between the two materials, and this must be accommodated by a network of interfacial dislocations with the lowest number of threading dislocations. It is thus important to understand the detailed mechanism of the formation of this network, in order to eventually reduce the dislocation density at the top of the layers.MOVPE growth is carried out on slightly misoriented, (3.5°) from (001) towards , Si substrates. Here we report on the effect of this misorientation on the interfacial defects, at a very early stage of growth. Only the first stage, of the well-known two step growth process, is thus considered. Previously, we showed that full substrate coverage occured for GaAs thicknesses of 5 nm in contrast to MBE growth, where substantially greater thicknesses are required.


1963 ◽  
Vol 10 (01) ◽  
pp. 106-119 ◽  
Author(s):  
E Beck ◽  
R Schmutzler ◽  
F Duckert ◽  

SummaryInhibitor of kallikrein and trypsin (KI) extracted from bovine parotis was compared with ε-aminocaproic acid (EACA): both substances inhibit fibrinolysis induced with streptokinase. EACA is a strong inhibitor of fibrinolysis in concentrations higher than 0, 1 mg per ml plasma. The same amount and higher concentrations are not able to inhibit completely the proteolytic-side reactions of fibrinolysis (fibrinogenolysis, diminution of factor V, rise of fibrin-polymerization-inhibitors). KI inhibits well proteolysis of plasma components in concentrations higher than 2,5 units per ml plasma. Much higher amounts of KI are needed to inhibit fibrinolysis as demonstrated by our in vivo and in vitro tests.Combination of the two substances for clinical use is suggested. Therapeutic possibilities are discussed.


2017 ◽  
Vol 13 (2) ◽  
pp. 4671-4677 ◽  
Author(s):  
A. M. Abdelghany ◽  
A.H. Oraby ◽  
Awatif A Hindi ◽  
Doaa M El-Nagar ◽  
Fathia S Alhakami

Bimetallic nanoparticles of silver (Ag) and gold (Au) were synthesized at room temperature using Curcumin. Reduction process of silver and gold ions with different molar ratios leads to production of different nanostructures including alloys and core-shells. Produced nanoparticles were characterized simultaneously with FTIR, UV/vis. spectroscopy, transmission electron microscopy (TEM), and Energy-dispersive X-ray (EDAX). UV/vis. optical absorption spectra of as synthesized nanoparticles reveals presence of surface palsmon resonance (SPR) of both silver at (425 nm) and gold at (540 nm) with small shift and broadness of gold band after mixing with resucing and capping agent in natural extract which suggest presence of bimetallic nano structure (Au/Ag). FTIR and EDAX data approve the presence of bimetallic nano structure combined with curcumin extract. TEM micrographs shows that silver and gold can be synthesized separately in the form of nano particles using curcumin extract. Synthesis of gold nano particles in presence of silver effectively enhance and control formation of bi-metallic structure.


2019 ◽  
Author(s):  
Alexander Giovannitti ◽  
Reem B. Rashid ◽  
Quentin Thiburce ◽  
Bryan D. Paulsen ◽  
Camila Cendra ◽  
...  

<p>Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side‑products. This is particularly important for bioelectronic devices which are designed to operate in biological systems. While redox‑active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side‑reactions with molecular oxygen during device operation. We show that this electrochemical side reaction yields hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), a reactive side‑product, which may be harmful to the local biological environment and may also accelerate device degradation. We report a design strategy for the development of redox-active organic semiconductors based on donor-acceptor copolymers that prevent the formation of H<sub>2</sub>O<sub>2</sub> during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte‑gated devices in application-relevant environments.</p>


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