Kinetics and Mechanisms for the Isomerization of Internucleosidic 3'-O-P-CH2-5' and 3'-O-P-CH(OH)-5' Linkages to Their 2',5'-Counterparts

2006 ◽  
Vol 71 (6) ◽  
pp. 859-870 ◽  
Author(s):  
Tuomas Lönnberg ◽  
Šárka Králíková ◽  
Ivan Rosenberg ◽  
Harri Lönnberg
Keyword(s):  
Hydrogen Bond ◽  
Hydroxy Group ◽  
Phosphorus Atom ◽  
Hydrolytic Stability ◽  
Model Compounds ◽  
Hydroxide Ion ◽  
Wide Ph Range ◽  
Acid Catalyzed ◽  
Ph Range

Isomerization of internucleosidic 3'-O-P-CH2-5' and 3'-O-P-CH(OH)-5' phosphonate linkages to their 2',5'-counterparts has been studied over a wide pH-range. The model compounds employed are phosphonate analogs of adenylyl-(3',5')-adenosine and adenylyl-(2',5')-adenosine having either adenosine ((R,S)-1, (R,S)-2) or 5'-deoxyadenosine (3, 4) bonded to the phosphorus atom through the C5'-atom. For comparative purposes, the hydrolytic stability of C5'-hydroxyphosphonate analogs derived from 2'-deoxyadenosine ((R,S)-5) has also been studied. In addition to the expected acid-catalyzed (pH < 3) and pH-independent reactions (pH 3-9), the diastereomeric C5'-hydroxyphosphonate analogs ((R,S)-1, (R,S)-2), but not their deoxy counterparts (3, 4), have been observed to undergo a hydroxide-ion-catalyzed isomerization around pH 11 (90 °C). Evidently a hydrogen bond between the dianionic phosphorane and the C5'-hydroxy group stabilize the phosphorane to such an extent that isomerization via kinetically invisible protonation to monoanion becomes possible. The mechanisms of the isomerization reactions taking place under various conditions are discussed.

ELECTROPHILIC DISPLACEMENT REACTIONS: XV. KINETICS AND MECHANISM OF THE BASE-CATALYZED PROTODEBORONATION OF ARENEBORONIC ACIDS

1963 ◽  
Vol 41 (12) ◽  
pp. 3081-3090 ◽  
Author(s):  
Henry G. Kuivila ◽  
Joseph F. Reuwer Jr. ◽  
John A. Mangravite
Keyword(s):  
Acid Catalysis ◽  
Low Ph ◽  
Ion Concentration ◽  
Buffer Concentration ◽  
Hammett Equation ◽  
Hydroxide Ion ◽  
Displacement Reactions ◽  
Acid Catalyzed ◽  
Ph Range ◽  
Kinetics Of

An investigation of the kinetics of the protodeboronation of benzeneboronic acid in water in the pH range 2.0 to 6.7 is described. In addition to the acid-catalyzed reaction studied earlier a reaction whose rate is independent of pH and one whose rate increases linearly with hydroxide ion concentration have been observed. The effect of malonate buffer concentration at low pH confirms the earlier observations of general acid catalysis. Changes in buffer concentration at pH 6.70 have no effect on rate indicating specific hydroxide ion catalysis. Effect of substituents in the ortho, meta, and para position of the benzene ring on the rate of protodeboronation have been examined. Ortho–para ratios for this reaction are high; possible reasons for this are discussed. The Hammett equation using σ correlates the rates for meta and para substituents.

Polarographic and spectrophotometric behaviour of some N-p-phenyl substituted benzamidines

1991 ◽  
Vol 56 (12) ◽  
pp. 2791-2799 ◽  
Author(s):  
Juan A. Squella ◽  
Luis J. Nuñez-Vergara ◽  
Hernan Rodríguez ◽  
Amelia Márquez ◽  
Jose M. Rodríguez-Mellado ◽  
...  
Keyword(s):  
Spectrophotometric Study ◽  
Absorption Bands ◽  
Electrochemical Parameters ◽  
Wide Ph Range ◽  
Group A ◽  
Substituent Constants ◽  
Ph Range ◽  
The Waves

Five N-p-phenyl substituted benzamidines were studied by DC and DP polarography in a wide pH range. Coulometric results show that the overall processes are four-electron reductions. Logarithmic analysis of the waves indicate that the process are irreversible. The influence of the pH on the polarographic parameters was also studied. A UV spectrophotometric study was performed in the pH range 2-13. In basic media some variations in the absorption bands were observed due to the dissociation of the amidine group. A determination of the pK values was made by deconvolution of the spectra. Correlations of both the electrochemical parameters and spectrophotometric pK values with the Hammett substituent constants were obtained.

High degradation efficiency of sulfamethazine with the dual-reaction-center Fe-Mn-SiO2 Fenton-like nanocatalyst in a wide pH range

2021 ◽  
Author(s):  
Manoj Kumar Panjwani ◽  
Qing Wang ◽  
Yueming Ma ◽  
Yuxuan Lin ◽  
Feng Xiao ◽  
...  
Keyword(s):  
Wastewater Treatment ◽  
Reaction Center ◽  
Degradation Efficiency ◽  
Heterogeneous Fenton ◽  
Wide Ph Range ◽  
Ph Range

The development of a heterogeneous Fenton-like catalyst, possessing high degradation efficiency in a wide pH range, is crucial for wastewater treatment. The Fe-Mn-SiO2 catalyst was designed, and prepared by a...

scholarly journals Defect-Rich Heterogeneous MoS2/rGO/NiS Nanocomposite for Efficient pH-Universal Hydrogen Evolution

Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 662 ◽  
Author(s):  
Guangsheng Liu ◽  
Kunyapat Thummavichai ◽  
Xuefeng Lv ◽  
Wenting Chen ◽  
Tingjun Lin ◽  
...  
Keyword(s):  
Graphene Oxide ◽  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Active Sites ◽  
Reduced Graphene ◽  
Heterogeneous Interfaces ◽  
Wide Ph Range ◽  
Ph Range ◽  
A Current ◽  
Poor Stability

Molybdenum disulfide (MoS2) has been universally demonstrated to be an effective electrocatalytic catalyst for hydrogen evolution reaction (HER). However, the low conductivity, few active sites and poor stability of MoS2-based electrocatalysts hinder its hydrogen evolution performance in a wide pH range. The introduction of other metal phases and carbon materials can create rich interfaces and defects to enhance the activity and stability of the catalyst. Herein, a new defect-rich heterogeneous ternary nanocomposite consisted of MoS2, NiS and reduced graphene oxide (rGO) are synthesized using ultrathin αNi(OH)2 nanowires as the nickel source. The MoS2/rGO/NiS-5 of optimal formulation in 0.5 M H2SO4, 1.0 M KOH and 1.0 M PBS only requires 152, 169 and 209 mV of overpotential to achieve a current density of 10 mA cm−2 (denoted as η10), respectively. The excellent HER performance of the MoS2/rGO/NiS-5 electrocatalyst can be ascribed to the synergistic effect of abundant heterogeneous interfaces in MoS2/rGO/NiS, expanded interlayer spacings, and the addition of high conductivity graphene oxide. The method reported here can provide a new idea for catalyst with Ni-Mo heterojunction, pH-universal and inexpensive hydrogen evolution reaction electrocatalyst.

Sign in / Sign up

Export Citation Format

Share Document