Local anti-infective agents and Preservatives – Medicinal Chemistry III B. Pharma 6th Semester

Local anti-infective agents and Preservatives

Contents

       Anti-infective
agents – classification 

       Local
Anti-infective agents – Introduction & Classification

       Mode
of action of various Local Anti-infective agents

       Synthesis  and specific uses of Furazolidone

       Preservatives
– Ideal characteristics & types

Learning Objectives

At the
end of this lecture, student will be able to

Describe the term “anti-infective agent”

Classify anti-infective agents

Enlist the ideal characteristics of Local anti-infective
agents (Germicides) & Preservatives

Classify Germicides & Preservatives

Describe the mode of action of Germicides

Introduction and Classification of anti-infectives

       Anti-infective
agents are those agents which are used in the treatment of infectious diseases

       Selective
toxicity is the main aim of modern “anti-infective therapy”

Classification:-

       Anti-infective
agents may be classified according to a variety of schemes, as the chemical
type of the compound the biological property and therapeutic indication

       A
combination of these classification schemes is used to classify the
anti-infective agents as

Classification of anti-infectives

Ø  Local Anti-infective agents:-

       Alcohols  – ethanol, isopropyl alcohol

       Phenols  – p-chlorophenol, hexachlorophene,
resorcinol, hexyl resorcinol

       Halogen
– containing compounds- Iodine tincture, Halozone.

       Oxidizing
agents – Hydrogen peroxide, Benzoyl peroxide.

       Cationic
surfactants – Benzalkonium chloride, Cetyl pyridium chloride

       Dyes
– gentian violet, Methyene blue.

       Nitrogen
compounds – Nitrofurazone, Furazolidone.

       Mercury
compounds – Nitromersol and Thimerosal

Ø  Preservatives :-

       p-hydroxy
benzoic acid derivatives – Methyl paraben, etc.,

       Miscellaneous
compounds as chlorobutanol, etc.,

Ø  Anti-fungal agents :-

       Anti-fungal
antibiotics – Nystatin, Candicidin, Hamycin, Griseofulvin, Amphotericin – B.

       Synthetic
anti-fungal agents

       Substituted
imidazoles: Clotrimazole, Metronidazole, Ketoconazole.

       Miscellaneous
compounds- Zinc propionate, Sodium Caprylate, Tolnaftate.

Ø  Urinary tract anti-infectives :-

       Quinolones
– Nalidixic acid, Norfloxacin, Ciprofloxacin, Perfloxacin

       Miscellaneous
– Nitrofurantoin.

Ø  Anti-tubercular agents:-

       Synthetic
anti-tubercular agents- PAS, INH, Ethanbutol, Pyrazinamide, etc.,

       Anti-tubercular
antibiotics – Cycloserine, Rifampicin.

Ø  Anti-viral agents:- as

       Amantadine
HCl, Acyclovir, Zidovudine

       Anti-AIDS
– Azathymidine, Suramin.

Ø  Anti – protozoal agents:- 

       Metronidazole,
Iodoquinol, Dimercaprol

Ø  Anthelmintics:-

       Diethyl
Carbamazine, Mebendazole, Niclosamide

       Anti-scabious
& anti-pedicular agents:-

       Benzyl
benzoate, Diethyl toluamide, Lindane.

Benzyl Benzoate

Diethyl toluamide

Lindane

Local Anti-infective agents (Germicides)

There are two primary sub-types

Antiseptics:-
kill (-cidal) or prevent the growth of (-static) micro-organisms when applied
to living tissues.

Ø  A
useful antiseptic must –

       Have
low toxicity so that it can be used directly on skin or wounds.

       Have
a rapid and sustained lethal action against micro-organisms.

       Have
low surface tension, so that it will spread into the wound.

       Have
the ability to retain activity in the presence of body fluids including pus.

       Be
non-irritating to tissues & non-allergic

       Lack
systemic toxicity when applied to the skin or mucous membrane.

       Have
no interference with the healing process of the wound.

Disinfectants:-

Ø  A
disinfectant is an agent that prevents transmission of infection by the
destruction of pathogenic micro-organisms when applied to inanimate objects.

Ø  An
ideal disinfectant:-

       Exerts
a rapid lethal action against all potentially pathogenic microorganisms &
spores.

       Have
good penetrating properties into organic matter.

       Should
be compatible with organic compounds (particularly soaps).

       Is
not inactivated by living tissues.

       Is
non-corrosive

       Is
esthetically pleasing (non-staining or odorless)

Alcohols
and related compounds:-

       Antibacterial
action is due to their ability to denature the bacterial proteins & inhibit
phosphorylation systems

Ethanol

       Clear,
Colorless, Volatile liquid, Burning taste, Characteristic pleasant odor

       Antiseptic

        Preservative

        Mild counterirritant

       Rubbing
alcohol is used as an

ü   Astringent

ü   Rubefacient

ü  Mild
local anesthetic

Isopropyl Alcohol

       Suitable
substitute for ethanol

       But
must not be ingested

       Primarily
as a disinfectant for the skin and for surgical instruments

       Bactericidal
in the concentration range of 50% to 95%

       A
40% concentration is considered equal in antiseptic efficacy to a 60% ethanol
in water solution

Formaldehyde Solution

       Formalin
is a colorless aqueous solution

       Used
as a disinfectant for surface sterilization

       Contains
not less than 37% w/v of formaldehyde (HCHO) with methanol added to retard
polymerization

       The
germicidal action of formaldehyde is slow but powerful

       The
mechanism of action: denaturation of proteins

ü  Direct
nonspecific alkylation of nucleophilic functional group (amino, hydroxyl, and
sulfhydryl) in proteins and nucleic acids to form carbinol derivatives

       Gutaraldehyde
used to sterilize surgical instruments and surfaces contaminated with hepatitis
virus

Phenol

       Phenol
(carbolic acid) is a colorless to pale-pink crystalline material with a
characteristic “medicinal odor

       Liquified
phenol is simply phenol containing 10% water

       Bacteriostatic
conc- 0.5%, Bactericidal-1%, fungicidal 1.5%

       MOA:
denaturation of proteins

       Phenols
& derivatives:-

p-Chlorophenol

       p-Chlorophenol
is used in combination with camphor in liquid petrolatum as an external
antiseptic and anti-irritant

Hexachlorophene

       Hexachlorophene,
2,2-methylene bis (3,4,6-trichlorophenol)

       2,2-
dihydroxy-3,5,6,3,5, 6-hexachlorodiphenylmethane

       Hexachlorophene
is easily adsorbed onto the skin and Enters the sebaceous glands

       Topical
application elicits a prolonged antiseptic effect

       Hexachlorophene
is used in concentrations of 2% to 3% in

        Soaps

       Detergent
creams

        Lotions

        Shampoos

       For
various antiseptic uses

       Effective
against gram-positive bacteria

       Many
gram-negative bacteria  are resistant

Resorcinol

       m-
Dihydroxybenzene (resorcin)

       Resorcinol
is only a weak antisepticit is used in 1% to 3% solutions

       Ointments
and pastes in concentrations of 10% to 20% for the treatment of skin conditions

ü  Ringworm

ü  Eczema

ü  Psoriasis

ü  Seborrheic

ü  Dermatitis

        Keratolytic agent

Hexylresorcinol

       4-hexylresorcinol

       Effective
antiseptic

       Bactericidal
and fungicidal properties

Oxidizing agents:-

       Oxidizing
agents that are of any value as germicidal agents depend on their ability to
liberate oxygen in the tissues

       MOA:
oxidation of sulphydryl groups of bacterial enzymes

       Hydrogen
peroxide  – H2O2

       Disinfectant
and sterilant

       Benzoyl
peroxide is both keratolytic and keratogenic

        It is used in the treatment of acne- exfoliant
,sebostatic

        Benzoyl peroxide induces proliferation of
epithelial cell leading to sloughing and repair

Halogen – containing compounds:

Iodine tincture

       It
is usually 2–7% elemental iodine, along with potassium iodide or
sodium iodide, dissolved in a mixture of ethanol and
water. 

       It
contains iodine which is an antiseptic. It is for use on
minor wounds, cuts and scrapes.

Povidone–Iodine

       Charge-transfer
complex of iodine with the nonionic surfactant PVP (poly vinyl pyrrolidine)

       Povidone–iodine
is used as an aqueous solution for pre-surgical disinfection of the incision
site

       Treating  infected wounds and damage to the skin

       It
is effective for local bacterial and fungal infections

Chlorine- Containing compounds

       All
the chlorophores act by releasing chlorine which oxidezes the sulphydryl groups
of bacterial enzymes and deactivates certain bacterial enzymes

       These
compounds release hypochlorous acid when dissolved in water in the presence of
acid – i.e HOCl is the active germicidal species.

        HOCl generates nascent oxygen to destroy the
vital cellular machinery of microorganism

Chlorhexidine

       Chlorhexidine,
also known as chlorhexidine gluconate (CHG), is a disinfectant and antiseptic
that is used for skin disinfection before surgery and to sterilize surgical
instruments-used both to disinfect skin of the patient and the hands of the
healthcare providers.

       It
is a germicidal mouthwash that reduces bacteria in the mouth. Chlorhexidine
gluconate oral rinse is used to treat gingivitis (swelling, redness, bleeding
gums).

Halazone

       P-dichlorosulfamoylbenzoic
acid

       Faint
chlorine odor

       The
sodium salt of halazone is used to disinfect drinking water

Cationic
surfactants:-

All cationic surfactants are quaternary ammonium compounds.
They are always ionized in water and exhibit surface active properties.

They form micelles by concentrating at the interface of
immiscible solvents-cationic head group has a high affinity for water and long
hydrocarbon tail has an affinity for lipids and nonpolar solvents

       Benzalkonium
chloride [Alkyl Benzyl dimethyl ammonium chloride is a mixture of alky benzyl
dimethyl ammonium chloride]

       Benzalkonium
chloride is a detergent, an emulsifier 
and a wetting agent

       It
is used as an antiseptic for skin and mucous membranes

       Cetyl
pyridinium chloride

       It
is used as a general antiseptic for 
intact skin

       Irrigation
of mucous membranes

        

Dyes

Gentian violet
[Hexamethyl-p-rosaniline chloride](crystal violet,methyl violet)

       Antiseptic
dye used to treat fungal infections of the skin (e.g., ringworm, athlete’s
foot).

       Also
has weak antibacterial effects and may be used on minor cuts and scrapes to
prevent infection.

Methylene blue
[3,7-Bis(dimethylamino)-Phenazathonium chloride

       Weak
antiseptic properties(bacteriostatic)

       Treatment
of cystitis  & urethritis

Nitrogen Compound:

Nitrofuran derivatives

       Nitrofurazone:
[5-Nitro-2-furfuraldehyde semicarbazone]

       Furazolidone
{3-[(5-nitrofurylidene) amino]-2-oxazolidinone}

       Has
bactericidal action against a relatively broad range of intestinal pathogens
including S.aureus, E.coli, Salmonella, Shigella, Proteus, Enterobacter and
Vibriocholerae
.

       Also
active against the protozoan Giardia Lamblia.

       Used
orally in the treatment of bacterial or protozoal diarrhea caused by
susceptible organisms.

Mercury compounds:

Mercurials

       From
early days, mercurial were used to treat skin infections & syphilis

       MOA:
reversible nature of sulfhydryl group blockage

       Nitromersol
[3-(hydroxy mercuri)-4-nitro-o-cresol]

       Thimerosal
{sodium [(o-carboxy phenyl) thio] ethyl mercury}

Mode of Action

Alcohols and related
compounds:-

       Ability
to denature proteins &  inhibit phosphorylation
systems

       As
the primary alcohol chain length increases, vanderwaal’s interactions increase
and the ability to penetrate microbial membranes increases.

       As
water solubility decreases the apparent anti-microbial potency diminishes.
Branching of the alcohol chain decreases anti-bacterial potency. Weaker
vanderwall’s forces brought about by branching do not penetrate bacterial cell
membranes as efficiently. Yet, 2-propanol is used commercially instead of
n-propyl alcohol as it is less expensive.

       The
germicidal action of formaldehyde is slow but powerful. It is the direct,
non-specific alkylation of nucleophilic functional groups (amino, hydroxyl,
sulphydryl) in proteins and nucleophilic acids to form ‘Carbinol’ derivatives.

Phenols and
Derivatives:-

       Phenols  “denatures bacterial proteins at low
concentrations”, “lysis of bacterial cell membranes at higher concentrations”

Oxidizing agents:-

       Germicidal
action is based on their ability to liberate oxygen in the tissues.

       All
these react in the tissues to generate oxygen and oxygen radicals. Oxidizing
agents are especially effective against anaerobic bacteria and can be used in
cleansing contaminated wounds.

Halogen-containing
compounds:-

       Iodine
acts to inactivate proteins by iodination of aromatic residues (Phenyl alanyl
and tyrosyl) and oxidation (sulphhydryl groups).

       Chlorine
released from compounds (Halozone) act by chlorination of amide nitrogen atoms
&oxidation of sulfhydryl groups in proteins

Cationic
Surfactants:-

       The
mechanism of action involves the dissolution of the surfactant into the
microbial cell membrane, destabilization and subsequent lysis.

       The
surfactants may also interfere with enzymes associated with the cell membrane.

Dyes:-

       Acts
on cell membranes. The difference in the susceptibility is related to the
cellular characteristics. The cationic dyes are active against gram +ve
bacteria and many fungi; gram –ve bacteria are generally resistant.

Nitrofurans:-

       The
mechanism of action of Nitrofurans are not fully understood.

       These
Nitrofurans are known to be mutagenic and carcinogenic under certain
conditions. The cellular effects may be due to DNA damage caused by metabolic
reaction products.

Preservatives

Ø  “Preservatives
are added to various dosage forms and cosmetic preparations to prevent
microbial contamination”

Ø  In
parenteral and ophthalmic preparations, preservatives are used to maintain
sterility in the event of accidental contaminations during use.

Ø  Ideal
preservative should be

       Effective
at low concentrations against all possible microorganisms

       Non-toxic

       Compatible
with other  constituents used in the
preparation

       Stable
for the shelf life of the preparation.

Ideal preservative does not exist – most preservatives have
some ideal features

       The
preservatives are of 2 types

Ø  Para-hydroxy
benzoic acid derivatives

Ø  Miscellaneous.

p-hydroxybenzoic acid
derivatives (Parabens):-

       Esters
of p-hydroxy benzoic acid have anti-fungal properties. Their toxicity to
human host is generally low due to rapid hydrolysis to p-hydroxy benzoic acid,
which is rapidly conjugated and excreted.

       Used
as preservatives for liquid dosage forms

       Preservative
effect increase with increase in molecular weight, but the methyl ester is more
effective against ‘Molds’, where as the propyl ester is more effective against
‘Yeasts’.

       Eg,
Methyl paraben – Methyl-p-hydroxybenzoate.

Others are propyl paraben (Propyl-p-hydroxybenzoate), Ethyl
paraben (Ethyl-p-hydroxybenzoate) and Butyl paraben (Butyl-p-hydroxybenzoate)

Other preservatives:-

       Chlorobutanol:
– 1,1,1-Trichloro-2-Methyl-2-Propanol

       Used
as bacteriostatic in injections, ophthalmics & intranasal preparations

       Sodium
benzoate-preservative in acidic liquid preparations

       Phenyl
carbinol- used in ointments & lotions as an antiseptic in the treatment of
pruritic infections

       Sodium
propionate, Benzyl alcohol, Phenyl ethyl alcohol (2-Phenyl ethanol), Benzoic
acid, Phenyl mercuric nitrate, Phenyl mercuric acetate, etc

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