Question

Hydroxyl radicals can pluck hydrogen atoms from molecules ("hydrogen abstraction"), and hydroxide ions can pluck protons from molecules (“deprotonation”). Write the reaction equations and Lewis dot structures for the hydrogen abstraction and deprotonation reactions for the generic carboxylic acid R-COOH with hydroxyl radical and hydroxide ion, respectively. Why is hydroxyl radical more toxic to living systems than hydroxide ion?

Short answer

The hydrogen abstraction reaction for the carboxylic acid R-COOH with hydroxyl radical (OH•) can be represented as: R-COOH + OH• → R-COO• + H2O. The deprotonation reaction for the carboxylic acid R-COOH with hydroxide ion (OH-) can be represented as: R-COOH + OH- → R-COO- + H2O. Hydroxyl radicals (OH•) are more toxic to living systems than hydroxide ions (OH-) because they are highly reactive and can cause oxidative stress in cells, leading to damage or death.

Step-by-step solution

Write the hydrogen abstraction reaction equation

The hydrogen abstraction reaction for the carboxylic acid can be written as follows: R-COOH + OH• → R-COO• + H2O Here, OH• is the hydroxyl radical and R-COOH is the given carboxylic acid.

Draw the Lewis dot structures for the hydrogen abstraction

The Lewis dot structures for the reactants and products in the hydrogen abstraction reaction are: Reactants: R-COOH OH• ..O .. : O-H || : C-O-H . Products: R-COO• H2O ..O .. : O:H || | C-O H

Write the deprotonation reaction equation

The deprotonation reaction for the carboxylic acid can be written as follows: R-COOH + OH- → R-COO- + H2O Here, OH- is the hydroxide ion and R-COOH is the given carboxylic acid.

Draw the Lewis dot structures for deprotonation

The Lewis dot structures for the reactants and products in the deprotonation reaction are: Reactants: R-COOH OH- ..O .. : O:H || | C-O-H .: Products: R-COO- H2O ..O .. : O:H || | C-O- H

Explain why hydroxyl radical is more toxic than hydroxide ion

Hydroxyl radicals (OH•) are more toxic to living systems than hydroxide ions (OH-) because they are highly reactive and can cause oxidative stress in cells, leading to damage or death. The hydroxyl radical is capable of damaging virtually all cellular components, including lipids, proteins, and DNA. This can lead to cellular malfunctioning and eventually cell death if these damages are not repaired. In contrast, hydroxide ions are not as reactive and do not cause such damage, making them less toxic to the living systems.

Key concepts

Hydrogen Abstraction

Hydrogen abstraction is a chemical process where a hydrogen atom is removed from a molecule by a radical species. This is common with hydroxyl radicals (OH•), which are highly reactive species. For instance, in the reaction of hydroxyl radicals with a generic carboxylic acid (R-COOH), a hydrogen atom is abstracted to form a carboxyl radical (R-COO•) and water (H2O).
This can be represented by the equation:

• R-COOH + OH• → R-COO• + H2O

The hydroxyl radical, with its unpaired electron, pulls the hydrogen atom away, facilitating the transformation of substances through the radical chain process. This step is critical in biochemical pathways and can lead to significant molecular changes within cells.

Deprotonation

Deprotonation involves the removal of a proton (H⁺) from a molecule, generally by a base such as a hydroxide ion (OH⁻). In the context of carboxylic acids like R-COOH, deprotonation occurs when these acids lose a proton, forming their conjugate bases (R-COO⁻) and water:

• R-COOH + OH⁻ → R-COO⁻ + H2O

The hydroxide ion acts as a base that accepts a proton from the acid, reversing its role from a typical oxygen donor to a receiver. This reaction changes the chemical nature of the molecule, influencing its reactivity and solubility. It plays a crucial role in biological systems during metabolism and cellular processes.

Carboxylic Acid Reactions

Carboxylic acids, characterized by the functional group -COOH, are versatile in chemical reactions. They readily participate in reactions like hydrogen abstraction and deprotonation.
In hydrogen abstraction, a hydroxyl radical interacts with the carboxylic acid, transforming it into a radical form.
In deprotonation, the acidic hydrogen is removed, forming a carboxylate ion.

• These reactions are vital in organic chemistry, contributing to the synthesis of numerous compounds.
• They can influence biological pathways like protein modification and lipid metabolism.

The structure and reactivity of carboxylic acids make them essential players in organic and biochemistry.

Lewis Dot Structures

Lewis dot structures are diagrams representing the valence electrons in a molecule's atoms. They serve as a simple model for understanding chemical bonding. In the context of the exercise, Lewis structures help visualize reactants and products during reactions.
For hydrogen abstraction:

• R-COOH starts with a traditional acid structure, with the -OH group bonded to the carboxylic carbon.
• After interaction with OH•, it forms R-COO•, altering the bonding.

For deprotonation:

• Initial and resulting species involve the transfer of electrons, seen in the Lewis diagrams.
• They illustrate the shift from neutral molecules to ionic species.

Lewis dot structures are crucial for visualizing electron shifts in reactions, aiding understanding of molecular transformations.

Reactive Oxygen Species

Reactive oxygen species (ROS) include highly reactive molecules like the hydroxyl radical (OH•) and hydrogen peroxide (H2O2). They are by-products of cellular metabolism but play significant roles in cell signaling and homeostasis.
However, uncontrolled ROS are harmful due to their reactivity, capable of oxidizing DNA, proteins, and lipids:

• The hydroxyl radical is particularly damaging because of its ability to instigate chain reactions, leading to oxidative stress.
• This stress is linked with several diseases, including cancer and neurodegeneration.

Cells manage ROS through antioxidants, but imbalance can lead to cellular damage and contribute to aging and various pathologies. Understanding ROS is critical for studies in oxidative stress and cellular protection mechanisms.