Detergent Samples Research Articles

Characterization of surfactant complex mixtures using Raman spectroscopy and signal extraction methods: Application to laundry detergent deformulation

This paper presents the analysis of surfactants in complex mixtures using Raman spectroscopy combined with signal extraction (SE) methods. Surfactants are the most important component in laundry detergents. Both their identification and quantification are required for quality control and regulation purposes. Several synthetic mixtures of four surfactants contained in an Ecolabel laundry detergent were prepared and analyzed by Raman spectroscopy. SE methods, Independent Component Analysis and Multivariate Curve Resolution, were then applied to spectral data for surfactant identification and quantification. The influence of several pre-processing treatments (normalization, baseline correction, scatter correction and smoothing) on SE performances were evaluated by experimental design. By using optimal pre-processing strategy, SE methods allowed satisfactorily both identifying and quantifying the four surfactants. When applied to the pre-processed Raman spectrum of the Ecolabel laundry detergent sample, SE models remained robust enough to predict the surfactant concentrations with sufficient precision for deformulation purpose. Comparatively, a supervised modeling technique (PLS regression) was very efficient to quantify the four surfactants in synthetic mixtures but appeared less effective than SE methods when applied to the Raman spectrum of the detergent sample. PLS seemed too sensitive to the other components contained in the laundry detergent while SE methods were more robust. The results obtained demonstrated the interest of SE methods in the context of deformulation.

An Assessment of the Levels of Phosphate in Local and Foreign Detergents in Kano Metropolis, Kano, Nigeria

Concentration of phosphate in some commercial detergents commonly used in homes, laundry services, schools and offices in Kano Metropolis have been determined. The analyses were carried out on both local and foreign detergents using a spectrophotometric method. The analysis was based on the formation of phosphomolybdate with added molybdate ion followed by its reduction with sodium sulphide in aqueous tetraoxosulphate (VI) acid medium. The system obeys Lambert-Beer’s law at 715 nm in the concentration range 0.30-12.24 mgdm -3 and the data were computed using percentage and t-test. The values obtained for local detergent samples were Bn (0.041%), Om (0.066%), Gn (0.013%), Bb (0.046%), Br (0.046%), Kl (0.035%), Bp (0.053%), Ep (0.010%), Zp (0.025%), Jb(0.014%), and Ar (0.042%) while those of the foreign detergents were Ps (0.005%), Td (0.042 %) ,Lk (0.027%), Ta (0.022%), Dm (0.007%), Bg (0.005%), Bs (0.026%), Kn (0.031%), and Lb (0.006%). The accepted level of phosphate in detergents is 0.5% (MSA, 2010). Thus, the concentration of these detergent samples fall within the set limit. This study has revealed that continuous use of these products could result in an increase in the phosphate levels in laundry discharges into soil, ponds, lakes and rivers. Excessive amount of phosphate has long been implicated in the eutrophication of surface water bodies, as such, to promote lake/river recovery and improve trophic status, it is imperative that phosphate loads in surface waters are reduced. Keywords: Chelated, Eutrophication, Phosphate, Phosphomolybdate, Synthetic detergent

Systematic analysis of protein-detergent complexes applying dynamic light scattering to optimize solutions for crystallization trials.

Detergents are widely used for the isolation and solubilization of membrane proteins to support crystallization and structure determination. Detergents are amphiphilic molecules that form micelles once the characteristic critical micelle concentration (CMC) is achieved and can solubilize membrane proteins by the formation of micelles around them. The results are presented of a study of micelle formation observed by in situ dynamic light-scattering (DLS) analyses performed on selected detergent solutions using a newly designed advanced hardware device. DLS was initially applied in situ to detergent samples with a total volume of approximately 2 µl. When measured with DLS, pure detergents show a monodisperse radial distribution in water at concentrations exceeding the CMC. A series of all-trans n-alkyl-β-D-maltopyranosides, from n-hexyl to n-tetradecyl, were used in the investigations. The results obtained verify that the application of DLS in situ is capable of distinguishing differences in the hydrodynamic radii of micelles formed by detergents differing in length by only a single CH2 group in their aliphatic tails. Subsequently, DLS was applied to investigate the distribution of hydrodynamic radii of membrane proteins and selected water-insoluble proteins in presence of detergent micelles. The results confirm that stable protein-detergent complexes were prepared for (i) bacteriorhodopsin and (ii) FetA in complex with a ligand as examples of transmembrane proteins. A fusion of maltose-binding protein and the Duck hepatitis B virus X protein was added to this investigation as an example of a non-membrane-associated protein with low water solubility. The increased solubility of this protein in the presence of detergent could be monitored, as well as the progress of proteolytic cleavage to separate the fusion partners. This study demonstrates the potential of in situ DLS to optimize solutions of protein-detergent complexes for crystallization applications.

Spectrophotometric Determination of Phosphate in Sugarcane Juice, Fertilizer, Detergent and Water Samples by Molybdenum Blue Method

A simple and sensitive spectrophotometric method has been developed for the determination of phosphate in mg per liter (parts per million) concentration range in sugarcane juice, water, fertilizer and detergent samples. The amount of phosphate is determined by molybdenum blue phosphorus method in conjugation with UV-visible spectrophotometer. This method is based on the formation of phosphomolybdate complex with the added molybdate followed by the reduction of the complex with hydrazine hydrate in aqueous sulphuric acid medium. The system obeys Lambert-Beer’s law at 840 nm in the concentration range 0.1-11 ppm. The colour intensity of the reduced phosphomolybdate solution is found to be proportional to the amount of phosphate present in sugarcane juice, water, fertilizer and detergent samples. The reaction conditions as well as the various experimental parameters affecting the development and stability of the coloured complex were carefully investigated and optimized for the quantitative determination of phosphate present in various samples. The optimized concentrations of various reagents used are 0.20N sulphuric acid, 0.02M hydrazine hydrate and 0.20% ammonium molybdate. The effect of time on the formation of phosphomolybdenum blue complex and addition of the order of the reagents was also studied. Scientific World, Vol. 11, No. 11, July 2013, page 58-62DOI: http://dx.doi.org/10.3126/sw.v11i11.9139

Evaluation of metal contents of household detergent samples from Turkey by flame atomic absorption spectrometry

The concentrations of cadmium, copper, chromium, cobalt, iron, lead, manganese, nickel, and zinc in detergent samples from Kayseri, Turkey were determined by flame atomic absorption spectrometry. HClO₄ (10 mL)/HNO₃ (10 mL) mixture was used for the digestion of household detergent samples. The correctness of the analytical procedures was checked with standard addition-recovery tests in different detergent samples for the investigated metal ions. The concentration ranges of the elements in the detergent samples were found as 17.2-60.1, 11.1-40.1, 2.5-32.3, 8.1-10.5, 7.2-21.6, 9.8-17.9, 1.7-3.8, 12.5-22.5, and 2.0-5.8 μg/g for iron, manganese, zinc, copper, lead, cobalt, cadmium, nickel, and chromium, respectively. The values found in this work were compared with some other studies around the world conducted on detergent samples.

Determination of four fluorescent whitening agents in laundry detergents by solid phase extraction combined with ultra-high performance liquid chromatography

A new method was established to determine three stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWA351, FWA85, FWA28 and FWA71) in laundry detergents by solid phase extraction (SPE) and ultra-high performance liquid chromatography with a diode array detector (UPLC-DAD). The fluorescent whitening agents were extracted from laundry detergents with 2% formic acid aqueous solution and methanol, and purified by WAX SPE column, and analyzed by UPLC-DAD on a Phenomenex Synergi Max-RP column (150 mm x 2.0 mm), employing acetonitrile-10 mmol/L ammonium acetate as the mobile phase in a gradient elution mode. The fluorescent whitening agents were qualitatively determined by retention time, and confirmed by the ultraviolet spectrum. The results indicated that the target analytes were in the range of 0.05-180 mg/L with the correlation coefficients (r) greater than 0. 999 3, and the method limits of quantification (MLOQ) of target analytes were ranged from 1.5 mg/kg to 15 mg/kg (S/N = 10). The feasibility of this method was demonstrated by the determination of FWAs in samples with spiked recoveries. The recoveries were in the range between 84.9% and 105%, and the precision (relative standard deviation, RSD) ranged from 3.2% to 6.1% (n = 6). Among the 15 samples analyzed, the rate of positive samples was 53.3%, over 1 000 mg/kg of FWA351 and FWA71 were detected. The method is simple, precise and has high recoveries for the determination of fluorescent whitening agents in laundry detergent samples.

The influence of sodium-polyacrilic macromolecular chain length to the powder detergents secondary washing performances

In order to investigate the influence of sodium-polyacrylate polymer as a co-builder in addition to the carbonate/zeolite builders in detergent builder system, secondary washing performances of powder laundry detergent containing equal percentage of sodium polyacrylate with the different weight average molar mass, Mw, have been examined. The value of the degree of whiteness, elongation at break, and total residue content are the most important secondary washing performances that significantly depend on sodium polyacrylates efficiency used as crystal inhibitors, stabilizers for suspended soil, and agents for soil redisposition prevention on fabric surface. The values of the whiteness and elongation at break for cotton fabrics increase with the increase of average weight molecular mass, Mw, up to the value of 70000 g/mol, while in the case of further increase of weight average molar mass up to the 250000 g/mol value of these characteristics begin to decline. The values of the total residue content after combustion indicate an increase in its content with the increase of weight average molar mass of 3000 to 70000 g/mol, while the highest value has been reached in the sample of detergent containing sodiumpolyacrilic with the weight average molar mass of 250000 g/mol. All detergent samples show no significant dependence of the secondary washing characteristics on the number of washing cycles.

Surface acoustic wave based analytical system for the detection of liquid detergents

A novel analytical sensing system has been designed for the characterization and discrimination of different detergents in water. This micro-sensor system could play a key role in the development of more efficient and environmentally-friendly washing machines by enabling the measurement of residual detergents. The sensing system comprises a dual shear-horizontal surface acoustic wave (SH-SAW) resonator sensor housed within a poly-dimethylsiloxane (PDMS) microfluidic chamber. Free and electrically shorted SAW designs were used to analyze synthetic samples of liquid detergents with varying concentrations. Two anionic surfactants, namely sodium dodecylbenzene sulfonate and sodium laureth sulphate, and one non-ionic surfactant, polyoxyethylene (9.5) t-octylphenol have been studied. Dilution tests have been performed in order to determine the sensitivity or detection limit of this liquid sensing system and have been found to be ca. 10 ppm. The SAW based sensor system correctly classified all three detergents through the use of the transient signal response. Because the sensor operates without the need for a selective chemical or biological coating, it should be both robust and reliable. We believe that such technology could be used to make environmentally-friendly and greener washing machines by minimizing the use of detergents and hot water.

Determination of endocrine-disrupting phenols in water samples by a new manual shaking-enhanced, ultrasound-assisted emulsification microextraction method

Manual shaking-enhanced, ultrasound-assisted emulsification microextraction (MS-USAEME) combined with ultraperformance liquid chromatography (UPLC) with UV detection has been developed for the determination of five endocrine-disrupting phenols (EDPs) in seawater samples and detergent samples: 4-tert-butylphenol (4-t-BP), 4-cumylphenol (4-CP), 4-tert-octylphenol (4-t-OP), 2,4-di-tert-butylphenol (2,4-di-t-BP) and 4-nonylphenol (4-NP). Optimum conditions were found to be: 25 μL 1-bromohexadecane as extraction solvent, 5 mL of aqueous sample and 1 g of NaCl to control the ionic strength; manual shaking for 10 s; ultrasonication for 1 min; centrifugation for 3 min at 5000 rpm (speed). For MS-USAEME, manual shaking for 10 s is essential for effective extraction when the ultrasonic extraction time is as brief as 1 min. The small volume of aqueous sample enhances the effect of manual shaking significantly. For seawater samples, the limit of detection (LOD) was 0.5-2.8 ng mL(-1), the limit of quantification (LOQ) was 1.8-9.3 ng mL(-1) with the relative standard deviation (RSD) in the range 4.2-10.3%. For detergent samples, the LOD was 0.4-2.4 ng mL(-1), LOQ was 1.6-8.2 ng mL(-1) and RSD 4.7-10.0%. The relative recovery was 96-109% for seawater samples and 81-106% for the detergent samples.

Proteolytic Enzymes in Detergents: Evidence of Their Presence through Activity Measurements Based on Electrophoresis

This laboratory exercise uses a problem-based approach to expose students to some basic concepts relating to proteins and enzymes. One of the main applications of enzymes at the industrial level is their use in the detergent market. The students examine a detergent sample to ascertain whether proteolytic enzymes are a component and, if so, which colored detergent granules contain them. A 4-hour standard exercise is described that can be easily modified to study a number of conditions that affect enzymatic activity. The students also become familiar with polyacrylamide gel electrophoresis as it is used to visualize the products of enzyme activity.

Detergents sensing system based on SH-SAW devices

We report on the design and characterization of a novel analytical sensing system for the detection and discrimination of various detergents. Our sensor system could play a key role in the development of more efficient and environmentally-friendly washing machines by enabling the measurement of residual detergents. The sensing device comprises of a dual shear horizontal surface acoustic wave (SH-SAW) resonator device housed in a poly- dimethylsiloxane (PDMS) microfluidic chamber. Unmetalized and electrically shorted device configurations were used to analyze synthetic samples of liquid detergents of different concentrations. The sensor system correctly classified all three detergents without the need for an additional biological or chemical coating.

Characterization of Nanming River (southwestern China) sewerage-impacted pollution using an excitation-emission matrix and PARAFAC

Nanming River, the largest urban river in Guizhou Province, southwestern China plateau, has been severely polluted for decades. This study characterizes the organic materials and their sources in the upstream and downstream waters by dissolved organic carbon (DOC), excitation emission matrix (EEM) spectroscopy, parallel factor (PARAFAC) analysis and photo-microbial experiments. DOC concentrations were low (47–120 μM C) upstream and relatively high (146–462 μM C) downstream. The PARAFAC studies on the sample EEM spectra demonstrated that the upstream dissolved organic matter (DOM) was mostly composed of one component that had a fulvic acid-like substance; downstream DOM was composed of two components with mixtures of tryptophan-like and fulvic acid-like substances. From the results of the sewerage drainage samples collected along the bank of the river, it is evident that both household detergent-like and protein-like or tryptophan-like substances are predominantly present, indicating that untreated sewerage effluents are the major sources of organic matter pollution in Nanming River. The degradation experiments conducted on river, sewerage drainage and commercial detergent samples demonstrated that the detergent-like and tryptophan-like substances are both photochemically and microbiologically more decomposable than fulvic acid-like materials under sunlight and dark incubations. These results suggest that the input of the untreated sewerage effluents along the streams is the major pollution source in Nanming River, and the fluorescent DOM was efficiently affected by both photochemical and microbial processes.

Simultaneous determination of one nonionic and two anionic surfactants using Fourier transform infrared spectrometry and multivariate analysis

A direct and reagent free procedure for simultaneous determination of sodium lauryl ether sulfate (SLES), coconut diethanol amide (CDEA) and linear alkylbenzene sulfonate (LABS) in undiluted samples of hand dishwashing liquids has been developed. This determination was carried out by using attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR) and multivariate analysis. An implementation of the PLS statistical approach to quantitative analysis of one nonionic and two anionic surfactants was applied to a set of mid-infrared spectra (1305–990 cm −1) recorded for commercial detergent samples and ternary standard solutions. An orthogonal calibration design for three components and five levels for standards were employed. Number of factors and scans and also the resolution were optimized. The statistical parameters such as the root mean square error of calibration (RMSEC), root mean square error of cross-validation (RMSECV), standard error of prediction (SEP) and relative standard deviation (R.S.D.) were evaluated. These parameters were obtained as: RMSEC 0.13, 0.20 and 0.14, RMSEV 0.09, 0.17 and 0.04 and SEP 0.12, 0.39 and 0.18 (g per 100 g) for SLES, CDEA and LABS, respectively. R.S.D. for five independent analyses were 1.69 for SLES, 3.76 for CDEA and 1.76 for LABS. The component linear correlation coefficients comparing actual and predicted concentrations of SLES, CDEA and LABS in some real samples were 0.9995, 0.9915 and 0.9974, respectively.

A Simple Spectrophotometric Determination of Phosphate in Sugarcane Juices, Water and Detergent Samples

A simple spectrophotometric method is developed for the determination of phosphate in sugar cane juice, water and detergent samples. The method is based on the formation of phosphomolybdate with added molybdate followed by its reduction with sodium sulphide in aqueous sulfuric acid medium. The system obeys Lambert‐Beer’s law at 715 nm in the concentration range 0.3‐12.24 ppm. Molar absorptivity, correlation coefficient and Sandell’s sensitivity values were found to be 6.1x103 mol-1 cm-1, 0.999 and 0.0156 µg cm-2 respectively. The results obtained were reproducible with acceptable standard deviation 3.7% and relative error 3.4%. For a comparison of the method phosphate present in various samples were also determined separately following an official method. The results of the developed method compare well with those of the official method.

The Use of Ion Chromatography for the Determination of Clean-In-Place-200 (CIP-200) Detergent Traces

Anion chromatography with conductivity detection was chosen as the analytical technique for the development of a cleaning validation method for clean-in-place (CIP) detergents. The method was developed and validated for the determination of traces of the detergent CIP-200. It was shown to be linear with a squared correlation coefficient (r2) of 0.9999 and the accuracy experiments presented average recoveries of 88.2% (area response factor) from stainless steel surfaces. The repeatability was found to be 1.6% and an intermediate precision of 1.9% across the range. The method was also shown to be sensitive with an average Detection Limit (DL) of 0.23 ppm and a Quantitation Limit (QL) of 0.70 ppm based on the amount of phosphate in the detergent sample. The phosphate signal was well resolved from typical ions encountered in water samples or any other interference presented from swabs and surfaces. The method was applied to cleaning validation samples and proved to be suitable for rapid and reliable quality control.

Online identification of the fluorescent whitening agent 4,4-bis(2-sulfostyrol)biphenyl using a sweeping technique combined with capillary electrophoresis/77 K fluorescence spectroscopy

The feasibility of combining the techniques of online concentration and CE/low-temperature fluorescence spectroscopy in the detection and identification of E,E-4,4'-bis(2-sulfostyryl)biphenyl (DSBP) in synthetic detergents at 77 K is demonstrated. The technique involves the use of sweeping-MEKC, and was used for the initial online concentration and separation, after which a cryogenic molecular fluorescence experiment was performed at 77 K. The proposed method not only permits the separation and detection of E,E-DSBP in a synthetic detergent sample, but also ensures that the online spectrum is readily distinguishable and can be unambiguously assigned at 77 K. The photoconversion and isomer separation of DSBP are also described.

Simultaneous determination of DTPA, EDTA, and NTA by capillary electrophoresis after complexation with copper

We present a method for simultaneous determination of the aminopolycarboxylic acids DTPA, EDTA and NTA in dishwashing detergents, paper mill waters, and natural waters by capillary electrophoresis (CE). The complexing agents were examined as their copper(II) complexes and separated by conventional CE with reversed polarity of the applied voltage. The optimum separation conditions were established by varying the pH and phosphate and tetradecyltrimethylammonium bromide (TTAB) concentrations in the run buffer. The separations were carried out in a fused-silica capillary (61 cmx75 microm i.d.) filled with phosphate buffer (80 mmol L(-1), TTAB concentration 0.5 mmol L(-1), pH 7.1, voltage -20 kV) using direct UV detection at 191 and 254 nm. With this CE method all the peaks in the electropherograms were properly separated, the calibration plots gave good correlation coefficients and all three complexing agents could be detected in less than 4 min. Linear calibration plots were obtained for CuDTPA, CuEDTA and CuNTA; limits of detection were 0.03 mmol L(-1) for all complexing agents and recoveries for all tested samples were within the range 104+/-7%. Results obtained from dishwashing detergent samples were found to be reliable and comparable with those from HPLC (R2=0.989) and UV-Vis (R(2)=0.985) methods.

LAUNDRY DETERGENTS AS A SOURCE OF HEAVY METALS IN IRISH DOMESTIC WASTEWATER

Concentrations of Cd, Cu and Zn in 175 detergent samples representing twenty-one brands of washing powders were analysed. Mean concentrations of 3.03 (± 0.50) μg Cd/g, 2.61 (± 1.22) μg Cu/g and 15.23 (± 7.26) μg Zn/g were recorded. The concentration of cadmium was much lower than previously reported. The daily contribution of metals from laundry washing are in the order of 54.5 μg Cd/ca/d, 47.0 μg Cu/ca/d and 274.1 μg Zn/ca/d. In Irish municipal wastewater the contribution from detergents of these metals are 31.9% for Cd, 0.24% Cu and 0.30% for Zn. This has important implications for sewage sludge disposal.

Detergent Powder: Investigation for Feasible Retrospective Dosimetry Using ESR Technique

An Electron Spin Resonance (ESR) study of radiation induced free radicals in the commonly used detergent powder (Surf), was conducted to examine its potential application for retrospective/high level dosimetry, including possible dating of the accidents. The radical ions present in the irradiated detergent powder were identified as arising predominantly from sodium tri poly phosphate (Na3P5O10) and sodium sulphate (Na2SO4). The physical mixture of sodium tri poly phosphate and sodium sulphate in 4:1 ratio was found to give an ESR response, similar to that of the detergent powder. These results suggest that the detergent powder can be used as a dosimeter in the 20 Gy to 18 kGy dose range, spanning over 3 orders of magnitude. The second derivative ESR spectra of the detergent powder irradiated to different doses showed that the relative yield of the radicals is independent of irradiation dose. The decay pattern of radicals when followed as a function of post irradiation days, lead to the idea about the contrasting decay characteristics of the radicals. From the ESR signals of the irradiated detergent samples, it is shown that radiation dose can be evaluated and the radiation incident can be dated with an accuracy of ±10%.

Properties of early photolysis intermediates of rhodopsin are affected by glycine 121 and phenylalanine 261.

Glycine 121 in transmembrane (TM) helix 3 and phenylalanine 261 in TM helix 6 of bovine rhodopsin have been shown to be critical residues for creating an appropriate chromophore binding pocket for 11-cis-retinal [Han, M., Lin, S. W., Smith, S. O., and Sakmar, T. P. (1996) J. Biol. Chem. 271, 32330-32336; Han, M., Lin, S. W., Minkova, M., Smith, S. O., and Sakmar, T. P. (1996) J. Biol. Chem. 271, 32337-32342]. To further explore structure-function relationships in the vicinity of receptor helices 3 and 6, time-resolved absorption difference spectra of rhodopsin mutants G121A, G121V, and G121L/F261A were obtained at 20 degrees C. Data were collected from 30 ns to 690 ms after laser photolysis with 7 ns pulses (lambdamax = 477 nm) and analyzed using a global exponential fitting procedure after singular value decomposition (SVD). For each mutant, the decay of its bathorhodopsin photoproduct (batho) into an equilibrium with its blue-shifted intermediate (bsi) was too fast to resolve (<20 ns). The reaction scheme found for the mutants G121A and G121L/F261A was batho/bsi --> lumirhodopsin (lumi) --> metarhodopsin I (MI) --> metarhodopsin II (MII). For G121V, an additional early 380 nm absorber, with a back-reaction to lumi, had to be included in the above scheme. For the three Gly121 mutants, the main pathway to reach the active MII state is via lumi and MI. This is in contrast to rhodopsin where the main pathway in detergent samples is via lumi and an early 380 nm absorber, MI380. From the accelerated batho decay present in all three mutants, we conclude that Gly121 is likely to participate in the earliest chromophore-protein interactions. In addition, bsi decay is further accelerated in mutant G121L/F261A, suggesting that Phe261 is an essential determinant of the protein processes involved in bsi decay.