A Critical Review of the Use of Surfactant-Coated ...

19 Aug.,2024

 

A Critical Review of the Use of Surfactant-Coated ...

Surfactant-Coated Organic Nanoparticles in Nanomedicine

During disease treatment, the administered molecule (drug) can exhibit a therapeutic effect only when it reaches the target site of action, such as an area of inflammation or a cancer tissue. However, when a free drug is administered into the bloodstream, its therapeutic efficacy is severely limited due to various problems including premature degradation, expulsion of the drug due to the reticuloendothelial system (RES, also called the mononuclear phagocyte system [MPS]), degradation due to instability of the drug, poor dispersibility, and poor accumulation at the site of action. The resulting non-selective tissue distribution of drugs is a major factor responsible for drug toxicity (for example, dose-limiting toxicity [DLT]).84 Organic nanoparticles, which are widely used in the field of nanomedicine, have potential to overcome the above problems because they can impart a variety of advantages to the encapsulated substances.85 For example, organic nanoparticles encapsulating anticancer drugs, genes, and proteins can be delivered selectively to the target site of action or specific cells while protecting the encapsulation from degradation and RES; such a technology increases therapeutic efficacy and reduces side effects and is called a &#;drug delivery system&#;.86&#;88 The constituents of the organic nanoparticles used in the drug delivery system are selected to be non-toxic or low-toxic to living organisms, and typical examples include biodegradable polymers (chitosan, gelatin, hyaluronic acid, PLGA, poly[alkyl cyanoacrylate], and poly-ε-caprolactone), solid lipids (cetyl palmitate, cholesterol, palmitic acid, stearic acid, and tristearin), and proteins (albumin, collagen, gliadin, legumin, protamine and silk) ( ).89&#;91 A number of methods for preparing organic nanoparticles have been reported, and the related mechanism has been reviewed in detail by Anton et al.74 For example, the emulsification solvent evaporation technique (polymer- and lipophilic drug-containing organic solvent is dispersed in surfactant-containing water to form an oil in water [O/W] emulsion as a template of nanoparticles, and then evaporated to precipitate polymeric nanoparticles containing the drug dispersed into the system) is widely used to prepare nanoparticles composed of biodegradable polymers, and the microemulsion method (oil phase containing low melting temperature lipid and lipophilic drug is dispersed in surfactant-containing water to form O/W microemulsion as a template of nanoparticles, which is then rapidly cooled to precipitate drug-containing solid lipid nanoparticles) is widely used to prepare nanoparticles composed of solid lipids.90,92 The preparation of PLGA nanoparticles by solvent evaporation technique is widely used, and the most commonly used surfactant in the preparation process is polyvinyl alcohol (PVA).93 Pisami et al used three different surfactants (PVA, sodium cholate [SC] [Figure 1], sodium taurocholate [TC], [ ]) in the preparation of PLGA nano/micro particles encapsulating lipophilic substances (perfluorooctyl bromide [PBOB]) by solvent evaporation technique (dichloromethane was used as the organic phase) and compared their detail of precipitation process by optical microscopy, confocal microscopy and transmission electron microscopy (TEM).94 The results showed that in the TC group, the precipitated particles showed acorn shaped (PBOB and PLGA individuals precipitated independently) morphology, while in the PVA group, both acorn and core-shell shaped morphologies were precipitated. As the reason for the difference in particle deposition morphology, they found that PVA forms a stable phase at the dichloromethane-water interface but has properties that prevent PLGA molecules from adsorbing to the interface, while TC does not allow other chemical species to adsorb at the interface. On the other hand, in the SC group, a mixed interface of PLGA molecules and surfactant was formed during particle formation, and particles with a core-shell shaped morphology were stably deposited in the system. Therefore, they concluded that when preparing particles by solvent evaporation technique, core-shell morphology was obtained if PLGA molecules could be adsorbed on the mixed interface, otherwise acorn shaped morphology was obtained. The coexistence of different surfactants may be useful in the formation of particles. Ramirez et al reported that when PLGA nanoparticles were prepared by the solvent evaporation technique, the presence of not only PVA but also other surfactant (SDS) leads to steric stabilization in the systems, resulting in the precipitation of PLGA nanoparticles with a smaller particle size than those prepared by PVA alone.95 Such findings suggest that surfactants play a critical role in the preparation of nanoparticles. The prepared nanoparticles were administered in vivo after their stability, interactions with proteins and cells have been thoroughly investigated in vitro.96

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Surface Charge and Protein Adsorption

The charge on the surface of the nanoparticles has an important influence on their intracellular localization. Compared to anionic and nonionic charged nanoparticles, cationic charged nanoparticles exhibit higher cellular uptake due to their enhanced adhesion to the surface of negatively charged cells by electrostatic attraction.97&#;99 It has also been reported that cationic charged nanoparticles incorporated into cells have the ability of endosomal escape. Lipid nanoparticles composed of ionized amine lipids with a pKa of 6&#;7 and tertiary amines have an electrically neutral surface charge in the blood (pH 7.4) but become cationic in the endosomal environment (pH < 6.5) after they are taken up into the cell. As a result, cationic charged nanoparticles fuse with the negatively charged endosomal membrane and release encapsulated drugs into the cytoplasm.100&#;102 By this mechanism, cationic surfactants such as cetyltrimethylammonium bromide (CTAB) and didodecyldimethylammonium bromide (DDAB) are used to provide a positive charge to the surface of nanoparticles ( ). Fay et al prepared cationic charged surfactant-coated nanoparticles (PLGA nanoparticles encapsulating plasmid DNA covered with cationic surfactant [DDAB]) and assessed their transfection efficiency into murine macrophage (RAW 264.7) cells, and observed an increase in cellular uptake and endosomal escape; transfection was achieved with a one thousandth amount of plasmid DNA compared to that of commonly used transfection reagent Lipofectamine®.103 In addition, cationic charged nanoparticles showed a stronger immune response than anionic charged and nonionic nanoparticles, which have attracted attention in recent years for the development of vaccines and application in the field of immunotheraphy.104,105 Kedmi et al prepared cationic charged surfactant-coated nanoparticles (small interfering RNA [siRNA] encapsulated in solid lipid nanoparticles coated with a cationic surfactant [1, 2-dioleoyl-3-trimethylammonium-propane (DOTAP)]) and observed the activation of the innate immune system in C57BL/6 mice.106 The results showed a 10- to 75- fold higher induction of type 1 helper (Th1) cytokine expression than the control particles (weakly anionic charged). However, cationic charged nanoparticles are more likely to disrupt cell membrane integrity and cause damage to mitochondria and lysosomes than anionic charged and nonionic nanoparticles, which raises concerns about their side effects.107 It has also been reported that the surface of cationic nanoparticles is prone to non-specific adsorption of albumin and alpha-1B-glycoprotein.108,109 Furthermore, as mentioned in section &#;Overview of Surfactant&#; of this review, the cationic surfactant itself has potential toxicity; approaches to avoid this toxicity have been reported, for example, Gossmann et al observed reduced side effects when the surface of PLGA nanoparticles coexisted with nonionic polymers (polyethylene glycol [PEG]) and cationic surfactant (DDAB) in vitro.110 The RES is actively involved in the phagocytosis of macrophages in the spleen, bone marrow, and liver.111&#;113 Nanoparticles administered into the bloodstream bind to proteins and antigens called opsonin, forming a corona (a complex of nanoparticles, proteins, and antigens), which is taken up by macrophages. This phenomenon is called &#;opsonization&#;, and the process involves apolipoprotein, albumin, fibrinogen, immunoglobulins, and complement components.114 The opsonized nanoparticles interact with receptors on the surface of macrophages and are transported to phagosomes and fused with lysosomes for degradation or elimination from the body.111 It has been reported that PLGA nanoparticles, which are not coated with any surfactant, are opsonized by non-specific adsorption of plasma proteins on their surface, which leads to their degradation in the body ( A).115 Moreover, targeting ligands present on the surface of the nanoparticles are masked by opsonization, which reduces their targeting ability. Salvati et al prepared silica nanoparticles modified with transferrin on its surface as a targeting ligand for receptor (transferrin receptor) on cancer cells and reported that the opsonized form of these nanoparticles lost their targeting ability.116 Hence, it is critical to avoid opsonization for effective targeting ability of nanoparticles in vivo and to reach the target site of action. Furthermore, it has been discovered that the nanoparticles coated with nonionic surfactants, such as poloxamers, avoid opsonization and predation by macrophages (this phenomenon is also called as &#;stealth effect&#;) ( B). Currently, PEG modification of nanoparticles is the most widely used method to impart stealth effect to nanoparticles, but the continuous administration of PEG-modified nanoparticles has raised concerns about the accelerated blood clearance (ABC) phenomenon (an immune response-induced mechanism to remove PEG-modified nanoparticles from the body).117&#;119 Su et al synthesized PEGylated surfactant by conjugation of surfactant (cholesteryl methyl amide) to PEG.120 They have reported that nanoemulsions composed of PEGylated surfactant showed weak ABC phenomenon in male Wistar rats. In the future, the properties of surfactants will be pursued more deeply, and surfactants that can modify the function of PEG and weaken the ABC phenomenon will be found. Jain et al prepared iron-encapsulated PLGA nanoparticles by optimizing the surface modification with a nonionic surfactant (poloxamer 188) using adsorption isotherm models (Langmuir, BET, Freundlich, Henderson, and Halsey models).121 The uptake of these surfactant-coated nanoparticles into murine macrophage (RAW 264.7) cells was compared with that of bare nanoparticles. The results revealed no cellular uptake of surfactant-coated nanoparticles after one hour of incubation. Liao et al prepared surfactant-coated nanoparticles composed of retinoic hydroxamic acid coated with nonionic surfactants (poloxamer 184 and 188) and observed their anticancer activity in subcutaneous melanoma (A375) mouse model.122 They reported that surfactant-coated nanoparticles exhibited a stealth effect in the body of mice, and showed enhanced anticancer activity due to increased accumulation in cancer cells and decreased accumulation in the liver during the 16 h observation period, compared to bare nanoparticles. The principle mechanism by which poloxamer-coated nanoparticles exerted a stealth effect is due to the influence of PEG and polyoxyethylene oxide (PEO) moieties in chemical structure of poloxamer.123,124 Surfactants and polymers with PEG, PEO, and polypropylene oxide (PPO) moieties are known to inhibit the adsorption of opsonins by building a hydrophilic barrier on the surface of the nanoparticles and by free movement and steric hindrance due to the construction of a polymer brush structure.125&#;128 This stealth effect has been observed not only with poloxamers but also with other nonionic surfactants having PEG and/or PEO moieties. For example, Zhao et al prepared surfactant-coated nanoparticles (gold nanoparticles covered with a nonionic surfactant [polysorbate 80]) and reported that adsorption of opsonization-related substances (bovine serum albumin [BSA], fibrinogen, γ-globulins, immunoglobulin G [IgG], and lysozyme) on surfactant-coated nanoparticles in phosphate buffer was inhibited, and no aggregation was observed for 24 hours.129 On the other hand, there is a theory of the mechanism of the stealth effect of nonionic surfactants related to change in the conformation of the opsonins attached to the surfactant. Torcello-Gómez et al prepared surfactant-coated nanoparticles (polystyrene nanoparticles covered with a nonionic surfactant [poloxamer 188]) and confirmed their adhesive dynamics with IgG, which is a typical example of opsonin.130 They reported that the adhesion of IgG on the surface of surfactant-coated nanoparticles was only slightly inhibited compared to bare nanoparticles, and 80% of the surface area was covered by IgG. However, the conformation of IgG that adhered to nonionic surfactants changed, suggesting that the suppression of opsonization is not due to adhesion but due to conformational changes in IgG. Although imparting the stealth effect to the nanoparticles by using nonionic surfactants is easy and bears low cost, but the potential problems need to be solved. One of such problem is the possibility of detachment of surfactants from the nanoparticles and causes unexpected side effects in vivo; the physiological effects of the autoxidized and hydroxylated products of nonionic surfactants, and their complement activation in vivo are largely unknown.76,131&#;133 One way to address these concerns might be to optimize the interaction between the encapsulated drug and the materials of the nanoparticles. Gagliardi et al compared zein and PLGA as suitable materials for the preparation of nanoparticles encapsulating lipophilic flavonoid (rutin).134 The results showed that the interaction between rutin and zein exhibited longer drug release kinetics in the zein group compared to the PLGA group, and this effect was most effectively demonstrated when sodium deoxycholate monohydrate (SD) was used in the preparation of nanoparticles. In the future, more useful surfactant-coated nanoparticles will be developed by further optimizing the compatibility of the encapsulated drug, nanoparticle material, and coating surfactant.

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Notes: (A) Bare nanoparticles. (B) Poloxamer 188 coated nanoparticles. (C) Polysorbate 80 coated nanoparticles.

Active and Passive Targeting

In addition to the adsorption and surface modification of the nanoparticles, the particle size is a major factor governing the behavior of nanomedicine. It is generally accepted that the desired particle size for solid particles administered as drugs for circulation in the bloodstream is 10&#;200 nm ( ).135 Particles smaller than 100 nm in size are known to avoid phagocytosis by the RES and have been reported to circulate in the bloodstream for a relatively long time.136&#;138 On the other hand, since the diameter of capillaries in the body is 3&#;9 μm, particles larger than that size can clog capillaries and unintentionally accumulate in organs with large surface areas of capillaries, such as the lungs.139 Kutscher et al found that particles with a size of 6 μm or larger accumulated in the lungs for more than a week when polystyrene microparticles of different particle sizes (2, 3, 6, and 10 μm) were administered intravenously to rats.140 In addition, particles larger than 400 nm in size were captured by splenic filtration, and then removed and degraded by red pulp macrophages.141 Conversely, it has been also reported that too small particle size can make it difficult to circulate in the bloodstream. Particles smaller than 15 nm are filtered out of the bloodstream by the kidneys and removed from the bloodstream.142 As the average effective pore size of normal vascular endothelial cell is approximately 5 nm, some reports suggest that particles with a size smaller than 5 nm leak out of vascular endothelial cells and accumulate at unintentional sites, causing them to disappear from the bloodstream in a short time.143 Particle size is also important in the development of cancer-targeting drug delivery systems. One of the most recognized cancer-targeting effects is the enhanced permeability and retention (EPR) effect, which was reported by Matsumura and Maeda in .144 The following two phenomena are collectively referred to as the EPR effect: (1) the presence of gaps in the new blood vessels around the tumor due to an incomplete vascular endothelial system, which allows nanoparticles to pass through the vessel wall and accumulate in the tissue; and (2) long-term accumulation of nanoparticles in the tumor tissue due to insufficient intratumoral exclusion system consisting of immature lymphoid tissue in cancer cells than in normal cells ( ). The EPR effect is referred to as &#;passive targeting&#; because it does not require surface modification with targeting ligand. The EPR effect is reported to be exhibited by particles having size of 100&#;400 nm.145 Based on this mechanism, a number of studies on cancer targeting chemotherapy using nanoparticles with a particle size of 400 nm or less have been reported to date.146&#;150 On the other hand, many researchers believe that EPR effect alone is not sufficient to achieve cancer-targeting therapeutic effect of nanoparticles, and further enhancement is required, as observed in some gastric and pancreatic cancers.151 Sindhwani et al reported in that the accumulation of nanoparticles in solid tumors is dominated via trans-endothelial pathways than by EPR effects, which has attracted much attention.152 In addition to the EPR effect, &#;active targeting&#; has been widely attempted to further enhance the therapeutic effects of nanoparticles. Active targeting refers to the modification of nanoparticles with targeting ligands (antibodies, aptamers, carbohydrates, macromolecules, proteins, and small molecules) for cancer cell-specific targets (antigens, lipid components, receptors, or proteins on the cell membrane). The drug encapsulated in the nanoparticles modified with the targeting ligand accumulates around the tumor tissue by the EPR effect (passive targeting) and is delivered and accumulated at the target site of cancer cells through response, affinity, and binding by the molecular site, shape, and stimulation (such as pH, temperature, and ultrasound) ( and ).153,154 Tumors with a volume of less than 100 mm3 have insufficient vascular endothelial gaps and are recognized as less effective for drug accumulation via EPR effect, while active targeting is regarded as effective in treating such small tumors and other diseases.155 Acharya et al prepared rapamycin-encapsulated PLGA nanoparticles.156  They reported that when their surface was modified with epidermal growth factor receptor monoclonal antibodies (EGFR mAb) (passive targeting + active targeting), their uptake into malignant breast cancer (MCF-7) cells was 13-fold higher than that of bare (passive targeting only) nanoparticles. Poom et al prepared PEG nanomicelles containing anticancer drug (paclitaxel) and reported that the accumulation of paclitaxel in rat tumor tissue decreased to 1% ID/g of tissue after 3 days when the PEG nanomicelles were administered (passive targeting only), whereas the drug accumulation of more than 5% ID/g of tissue was maintained even after 5 days when the PEG nanomicelles modified with folate ligands were administered (passive targeting + active targeting).157 However, excessive surface modification of nanoparticles with targeting ligands is thought to result in poor targeting to cancer cells due to the following factors: (1) decrease in the stealth effect due to the reduced surface exposure of molecular sites such as PEG, PEO, and PPO, (2) decrease in the EPR effect with the increase in particle size, (3) reduced diffusion of nanoparticles in cancer tissue, (4) decrease in the ability to bind to cancer cell-specific targets due to steric hindrance between targeting ligands, and (5) a decrease in the number of particles taken up by increasing the receptor occupancy per particle ( ).158 Therefore, it is suggested to optimize the density of the targeting ligands for specific cancer cell targeting for maximum interaction between nanoparticles and target cells. Recently, several nanomedicine products based on nanoparticles have been approved by the Food and Drug Administration (FDA).159,160 Although the field of research on nanoparticle-based drug delivery systems is developing rapidly, there are many concerns that need to be considered in the future, especially when nanoparticles are not distributed within the tumor microenvironment depending on the condition of cancer,161 expression of surface receptors varies depending on the diversity of cancer (for example, active targeting not working well for cancer stem cells),162 and acquisition of drug resistance in cancer.163

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Notes: (A) Normal vasculature. (B) Passive targeting in tumor vasculature. (C) Active targeting in tumor vasculature. (D) Types of active targeting ligands for nanoparticles and its considerations for optimization of their efficacy. Notes: (B, C) Adapted from Tran S, DeGiovanni P, Piel B, et al. Cancer nanomedicine: a review of recent success in drug delivery. Clin Transl Med. ;6(1):44. doi:10./s-017--0.153(D) Adapted from Advanced Drug Delivery Reviews, 143, Alkilany AM, Zhu L, Weller H, et al, Ligand density on nanoparticles: a parameter with critical impact on nanomedicine, 22&#;36, Copyright , with permission from Elsevier.158

Brain Targeting

Even if a substance is proven effective in treating brain tumors, neurodegenerative diseases and central nervous system diseases, to the most important challenge is to deliver it to the brain. Effective therapeutic antibodies are being developed to target brain diseases, however, brain delivery approach for these antibodies while maintaining their shape has yet to be developed.164 Nanotechnology is potentially used to protect encapsulated substances. Establishing technologies for transporting nanoparticles to the brain is one of the greatest obstacles in the field of nanomedicine. The major obstacle is the presence of the blood-brain barrier (BBB), which exists between the central nervous system and the blood, and greatly restricts the transport of substances to the brain. Substances circulating in the bloodstream can only pass through the BBB if these are (1) hydrophobic molecules of weight below 450 Da or (2) transported via endogenous transporters present in the BBB.165,166 Therefore, regardless of the type of material used to prepare nanoparticles; it is difficult for them to reach the brain by simply injecting them intravenously in their original state. On the other hand, it has been reported that nonionic surfactant (for example, polysorbate 80)-coated nanoparticles with active targeting function could reach the brain; although the detailed mechanism of transport of nanoparticles into the brain by modification with polysorbate 80 is still unclear. The current prevailing theory is that apolipoprotein adsorption at the polysorbate 80 site of surfactant-coated nanoparticles circulating in the bloodstream that crosses the BBB through receptor-mediated transcytosis ( ).167,168 The use of nonionic surfactants such as polysorbate 80 may also help nanoparticles to accumulate in the brain for a long time due to their inhibitory effect on P-glycoprotein (Pgp/ABCB1, a mechanism of foreign body efflux in the brain).169,170 Other substances that use this mechanism of brain transport are poly (butyl cyanoacrylate) (PBCA) and PLGA.171 Wilson et al prepared surfactant-coated nanoparticles (rivastigmine-encapsulated PBCA nanoparticles coated with polysorbate 80) and quantitatively evaluated their transport to the brain.172 They administered surfactant-coated nanoparticles to a group of rats via tail vein injection and reported a four-fold increase in the concentration of rivastigmine in the brain one hour after administration compared to the group receiving free drug. Tahara et al prepared surfactant-coated nanoparticles (coumarin-6 encapsulated PLGA nanoparticles coated with polysorbate 80) and quantitatively evaluated their transport to the brain.173 They reported that the surfactant-coated nanoparticles administered to a group of rats via tail vein injection showed a two-fold increase in the concentration of coumarin-6 in the brain one hour after administration, compared to a group of rats being administered bare nanoparticles (without surfactant coating). Furthermore, they reported that the increased transport to the brain was specific only to the nanoparticles coated with polysorbate 80, and similar result was not demonstrated by chitosan or other nonionic surfactants (poloxamer 188). The transport of surfactant-coated nanoparticles into the brain has also been studied using surfactants other than polysorbate 80, such as polyoxyethylene esters of 12-hydroxystearic acid (Solutol® HS15, BASF corporation, Ludwigshafen, Germany) and D-alpha-tocopherol polyethylene glycol succinate, however, the mechanism of their transport is not clear.174,175 Many studies on brain transport of surfactant-coated nanoparticles have reported only blood concentration and brain accumulation, but it is also important to evaluate the drug accumulation in other non-specific organs. Miyazawa et al prepared surfactant-coated nanoparticles (PLGA nanoparticles encapsulated with β-carotene and coated with polysorbate 80), and quantitatively evaluated their accumulation in the brain and other organs in rats via tail vein administration.176 They reported that the surfactant-coated nanoparticles administered group showed higher drug accumulation in the lungs (350-fold higher concentration compared to the group of bare nanoparticles) than in the brain after one hour of administration. A similar phenomenon has been reported in the study by Tröster et al, who prepared polymethyl methacrylate resin nanoparticles coated with various nonionic surfactants (polysorbates [20, 60, and 80], poloxamers [184, 188, 338, 407, and 908], and polyoxyethylene lauryl ether [Brij 35]) and administered them to rats via tail vein to compare their accumulation in organs over time.177 In their report, compared to the bare nanoparticles, the particles coated with polysorbate 80 had an approximately 11-fold increase in accumulation in the lungs and a nine-fold increase in accumulation in the brain after 30 min of administration. They also reported that approximately half of the particles that had accumulated in the lungs migrated to the liver two hours after administration. Therefore, increasing drug concentrations at the target site of action can enhance the desired therapeutic effect, but significant toxicity may also occur because of the increased drug accumulation in non-specific organs.

While polysorbates and poloxamers have been reported to perform such useful functions, there are concerns about their side effects that cause cell membrane damage and cytotoxicity.178 Recently, potential surfactants other than poloxamer and polysorbate have been discovered for brain targeting. For example, Jeong et al prepared surfactant-coated nanoparticles (PLGA nanoparticles encapsulated with recombinant human erythropoietin [rhEPO] and coated with sodium cholate or polysorbate 80) and evaluated their cellular uptake (human neuroblastoma [SH-SY5Y] cells) and evaluated inhibition rate of glutamate-induced neurotoxicity.179 The results showed that the sodium cholate-coated nanoparticle group was taken up by SH-SY5Y cells and further reduced glutamate-induced neurotoxicity with less toxicity than the polysorbate 80-coated group. They also examined the efficacy of these nanoparticles in vivo experimental stroke model mice and reported that the symptoms were reduced.180 It is expected that a variety of surfactants targeting the brain will be developed in the future. In recent years, the importance of &#;inter-organ communication,&#; which considers treatment based on the interaction of the drug with entire body&#;s organs, and not just the individual organ has been recognized; this concept will also be essential for the development of surfactant-coated nanoparticles.181

Winning the Hard Water Battle: Optimizing Detergent ...

Introduction

Hard water causes a number of undesirable consequences for homeowners, particularly when it comes to laundry. The presence of calcium and magnesium ions in hard water negatively affects detergent performance, leading to inefficient cleaning and potential damage to clothing and textiles. In this article, we will explore the nature of water hardness, its impact on detergents, and strategies to optimize detergent formulas to deliver excellent cleaning results even in the presence of hard water.

Understanding Water Hardness

A. Definition of water hardness

Water hardness is primarily defined by the concentration of calcium and magnesium ions present in the water. The hard water minerals interact with various chemicals in the detergents, adversely affecting their cleaning performance.

B. Common causes and sources of hard water

Hard water minerals usually come from groundwater sources, such as wells or aquifers, where water passes through rocks rich in calcium and magnesium. The level of water hardness can vary depending on the geological makeup of the region and the source of the water supply.

C. Measuring water hardness levels

Water hardness is generally measured in grains per gallon (gpg) or parts per million (ppm) of calcium carbonate (CaCO3) equivalent. Water with a hardness level of more than 17.1 ppm is considered hard, while anything above 180 ppm is classified as very hard water.

How Water Hardness Affects Detergent Performance

A. Interaction between hard water ions and detergents

Hard water minerals form insoluble compounds with soap, reducing the efficacy of cleaning agents. Additionally, they can interact with surfactants in synthetic detergents and decrease their ability to form micelles, which are crucial for trapping dirt and grease.

B. Impact on cleaning properties

The presence of hard water minerals can reduce the overall cleaning performance of detergents. Clothes washed in hard water may not come out as clean as they should, and the buildup of minerals on fabrics can leave them feeling stiff and rough.

C. Influence on foamability and foam stability

Hard water can affect the formation and persistence of foam in detergents. As a key property for effective cleaning, foam aids in the suspension of dirt particles and their subsequent removal. Hard water interferes with foam by reducing foamability and stability, leading to diminished cleaning action.

Common Hard Water Problems in Laundry

A. Minerals buildup and fabric stains

Hard water can cause the buildup of mineral deposits on clothing and fabrics, leading to discoloration and stiffness. This buildup can also leave distinguishable chalky white or gray stains on clothing, especially on dark-colored fabrics.

B. Damage to clothing and textiles

Continual exposure to hard water during the laundering process can cause fibers in fabrics to weaken and break, leading to a shorter lifespan for clothing and textiles.

C. Skin irritation and sensitivities

The residual minerals left on fabric by hard water can cause skin irritation and exacerbate existing skin sensitivities, such as eczema or psoriasis.

Detergent Formulation: Key Components and Surfactants

A. Nonionic surfactants

Nonionic surfactants are a common ingredient in detergent formulations. They are less affected by the presence of multivalent ions (hard water) than other types of surfactants and are generally milder on skin, dyes, and fabrics. Cocamide DEA, Fatty Alcohol Polyoxyethylene Ether(AEO-7/ AEO-9), and Alkyl Polyglycoside are the common nonionic surfactants widely used in detergent formulas, for their excellent hard-water resistance and other properties.

B. Anionic surfactants

Anionic surfactants are widely used in detergents due to their good cleaning performance and high levels of foam generation. However, they can be more susceptible to the negative effects of hard water minerals. It&#;s worth noting that different anionic surfactants have varying levels of hard water sensitivity, which can influence their effectiveness in hard water conditions.

Linear Alkyl Benzene Sulphonic Acid (LABSA), Sodium Lauryl Ether Sulfate (SLES), Sodium Lauryl Sulfate (SLS), and Alpha Olefin Sulphonate (AOS) are the four most commonly used anionic surfactants in detergents. In terms of their sensitivity to hard water, LABSA has the highest sensitivity, followed by SLES and SLS, which have similar sensitivity levels. AOS has the lowest sensitivity among these four surfactants. This ranking of hard water sensitivity can be represented as: LABSA > SLES &#; SLS > AOS.

C. Key role of builders in aiding the cleaning process

Builders are components in detergents that help to enhance the overall cleaning performance. They act in various ways, such as softening the water by binding to hard water ions and maintaining the appropriate pH levels for effective cleaning.

Optimizing Detergent Formulas for Hard Water

A. Using surfactants with low sensitivity to calcium and magnesium ions

Selecting surfactants that are less affected by hard water minerals can improve cleaning efficiency. To achieve the best cleaning performance in different conditions, including hard water, it is recommended to formulate with a primary surfactant (usually an anionic surfactant, LABSA for powder detergents, and SLES for liquid surfactants) and combine it with one, two, or even three secondary surfactants to achieve a synergistic effect. Some of the common effective surfactant combinations in detergents include:

Type of DetergentSurfactant CombinationApplicationPowder DetergentsLABSA + AOSHigh-foaming hand washingLABSA + SLSHigh-foaming hand washingLABSA + AEO-9Low-foaming machine washingLiquid DetergentsLABSA + SLES + CDEAHigh-foaming hand washingLABSA + SLES + CAPBHigh-foaming hand washingSLES + CDEAHigh-foaming hand washingSLES + CAPBHigh-foaming hand washingSLES + AEO-9Low-foaming machine washingSurfactant Combinations for Optimal Detergent Performance in Hard Water Conditions

By incorporating these surfactant combinations, detergents can be tailored to suit different application requirements, such as high-foaming hand washing or low-foaming machine washing, while also ensuring efficient and effective performance in hard water conditions.

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B. Incorporating chelating agents and water softening agents

Chelating agents, such as ethylenediaminetetraacetic acid (EDTA), are usually added to liquid detergents to sequester hard water ions and prevent them from interfering with the cleaning action. By binding to the calcium and magnesium ions, chelating agents effectively neutralize the effects of hard water.

However, in powder detergents and soaps, Sodium tripolyphosphate (STPP) or 4A zeolite is commonly added as a water softener. The addition ratio is often not small, commonly ranging from 5% to 15%. This is because, in powder detergents, LABSA is often the primary surfactant, and in bar soaps, soap (such as sodium stearate, sodium palmitate, or sodium oleate) is the primary surfactant. Both LABSA and soap are highly sensitive to hard water, so a significant amount of water softener is necessary to guarantee effective cleaning performance.

The use of chelating agents and water softening agents in detergents helps to mitigate the negative effects of hard water on the cleaning process, ensuring that the surfactants can work effectively and provide satisfactory results.

C. Adding suspension agents to prevent re-depositing on fabrics

Incorporating suspension agents in detergent formulations can help keep soil particles and mineral deposits suspended in the water, preventing their reattachment to fabrics and ensuring a cleaner wash.

For powder detergents, carboxymethyl cellulose (CMC) is commonly used as a suspension agent. CMC is a water-soluble polymer derived from cellulose, exhibiting excellent suspension and stabilization properties. It effectively prevents soil particles and minerals from settling back onto fabrics during the washing process and contributes to a cleaner and brighter appearance of the washed items.

In the case of liquid detergents, sodium polyacrylate is typically employed as a suspension agent. Sodium polyacrylate is a super-absorbent polymer that can absorb and retain large amounts of water, forming a gel-like substance. This property makes it particularly effective in creating a stable suspension of soil particles and mineral deposits in the wash water, preventing them from settling back onto the fabrics and maintaining the overall cleaning performance of the detergent.

In addition to CMC and sodium polyacrylate, other suspension agents like xanthan gum, guar gum, and hydroxyethyl cellulose (HEC) can also be used in detergent formulations for similar purposes. By incorporating effective suspension agents in detergents, manufacturers can create products that deliver enhanced cleaning results, even in challenging hard water conditions.

D. Implement Enzyme-Enhanced Formulations

Enzymes are biological catalysts that can enhance cleaning efficiency, particularly in cold and hard water conditions, by targeting specific stain components that might be harder to remove due to the presence of minerals. Some commonly used enzymes in detergent formulations include proteases, lipases, and amylases, each targeting different types of stains. The use of enzyme-based detergents in hard water can improve overall cleaning performance, as the enzymes work synergistically with surfactants to break down and remove challenging stains that can be more stubborn when minerals are present in the wash water.

Comparative Performance of Powder and Liquid Detergents in Hard Water

A. Pros and Cons of Powder Detergents

Advantages:

  1. Powder detergents tend to offer more potent cleaning power and are often more cost-effective than liquid detergents.
  2. They are particularly efficient in removing dirt and grime from fabrics.

Disadvantages:

  1. The primary surfactant in powder detergents, LABSA, can be negatively affected by calcium and magnesium ions in hard water.
  2. To maintain effective cleaning in hard water conditions, powder detergents may require an increased dose (10-15% to >30%) than what is typically recommended.

B. Pros and Cons of Liquid Detergents

Advantages:

  1. Liquid detergents are often considered more convenient and easier to use than powder alternatives.
  2. They dissolve well in water and can be more effective at removing oil and grease stains.

Disadvantages:

  1. The efficacy of liquid detergents in hard water conditions may be somewhat reduced in comparison to soft water conditions.
  2. To achieve better cleaning results in hard water, the use of additives or treatment systems may be necessary.

Tips for Washing Clothes in Hard Water

A. Choosing the right detergent for hard water

Selecting a detergent designed specifically for hard water conditions can help improve cleaning performance. Look for products that contain water softeners or chelating agents to minimize the impact of hard water minerals.

B. Adding water softeners and appropriate dosages

Water softeners can be added to the wash cycle to help combat the negative effects of hard water. Follow the manufacturer&#;s instructions to determine the appropriate dosage for your water hardness level.

C. Proper water temperature and load size for optimal cleaning performance

Using the proper water temperature and adhering to recommended load sizes can improve the cleaning efficiency of detergents in hard water conditions. Hot water is generally more effective at dissolving hard water minerals, but take care to ensure you are using the recommended temperature settings for the specific fabrics being laundered.

DIY Solutions: Utilizing Vinegar in Hard Water Laundry

A. Benefits of using vinegar in the wash cycle

White vinegar is a natural and cost-effective solution for combating hard water in laundry. It can help to dissolve mineral deposits, soften fabrics, and even neutralize any lingering odors.

B. Detailed instructions for incorporating vinegar into laundry routines

Add approximately half a cup (120 ml) of white vinegar to the washing machine during the rinse cycle. It is important to note that vinegar should not be mixed directly with bleach or detergents containing bleach, as this can create harmful fumes.

C. Potential limitations and drawbacks

While vinegar is a practical DIY solution for hard water laundry issues, it may not be as effective as specially formulated detergents or water softening systems. It may also not be suitable for fabrics that are sensitive to high-acid solutions.

Conclusion

In conclusion, water hardness presents substantial obstacles to detergent performance, resulting in less effective or even harmful laundry outcomes. As industry insiders, understanding the intricacies of hard water, its impact on detergents, and approaches for optimizing detergent formulas can enable us to develop innovative solutions for tackling hard water challenges. By creating and promoting the appropriate products and best practices that address hard water issues, we can provide value to consumers, enhance their laundry experience, and secure a competitive edge in the market, ultimately resulting in long-term benefits for our business, as well as for clothing, textiles, and appliances.

Frequently Asked Questions

1. What is the ideal detergent for hard water?

An ideal detergent for hard water should contain water softeners and chelating agents to minimize the impact of hard water minerals. Opting for enzyme-based or low-pH formulas may also help in tackling hard water challenges.

2. Can ion-exchange water softeners improve detergent performance in hard water?

Yes, ion-exchange water softeners can improve detergent performance by exchanging calcium and magnesium ions for sodium ions, thereby softening the water and allowing detergents to work more effectively.

3. How can I maintain the efficiency of my washing machine in hard water conditions?

Proper maintenance, including regular cleaning, inspection of hoses and connections, and using the appropriate detergent formulas designed for hard water, can help maintain the efficiency of your washing machine in hard water conditions.

4. How can I determine the hardness of my water at home?

There are various methods to measure water hardness at home, including test strips, water hardness testing kits, or consulting your local water provider. Understanding the hardness level of your water can help you make informed decisions about the type and dosage of detergents to use for optimal cleaning performance.

5. Can I use softening agents in combination with enzymes for improved cleaning in hard water conditions?

Yes, combining softening agents with enzyme-based detergents can provide a synergistic effect, improving overall cleaning efficiency in hard water. The softening agents help reduce the negative impact of mineral ions, allowing the enzymes to work effectively to break up and remove stubborn stains. Always follow the manufacturer&#;s recommendations regarding the use and dosage of detergent additives.

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