The microstructure and bulk rheology of human cervicovaginal mucus are remarkably resistant to changes in pH.

The protective barrier, lubricant, and clearance functions of mucus are intimately coupled to its microstructure and bulk rheology. Mucus gels consist of a network of mucin biopolymers along with lipids, salts, and other proteins and exhibit similar biochemical and physical properties across diverse mucosal surfaces. Nevertheless, mucus is exposed to a broad range of pH values throughout the human body. Protein functions are typically sensitive to small changes in pH, and prior investigations using reconstituted, purified mucin gels suggested mucus undergoes a transition from a low-viscosity liquid at neutral pH to a highly viscoelastic solid at low pH. We sought to determine whether those observations hold for fresh, minimally perturbed human mucus ex vivo by using different-sized muco-inert nanoparticles to probe microstructure and cone-and-plate rheometry to measure bulk rheology. We demonstrate that both the microstructure and bulk rheology of fresh, undiluted, and minimally perturbed cervicovaginal mucus exhibit relatively minor changes from pH 1-2 to 8-9, in marked contrast with the pH sensitivity of purified mucin gels. Our work also suggests additional components in mucus secretions, typically eliminated during mucin purification and reconstitution, may play an important role in maintaining the protective properties of mucus.

Direct analysis in real time mass spectrometry for analysis of sexual assault evidence.

RATIONALE: Sexual assault crimes are vastly underreported and suffer from alarmingly low prosecution and conviction rates. The key scientific method to aid in prosecution of such cases is forensic DNA analysis, where biological evidence such as semen collected using a rape test kit is used to determine a suspect's DNA profile. However, the growing awareness by criminals of the importance of DNA in the prosecution of sexual assaults has resulted in increased condom use by assailants as a means to avoid leaving behind their DNA. Thus, other types of trace evidence are important to help corroborate victims' accounts, exonerate the innocent, link suspects to the crime, or confirm penetration. METHODS: Direct Analysis in Real Time Mass Spectrometry (DART-MS) was employed for the comprehensive characterization of non-DNA trace evidence associated with sexual assault. The ambient ionization method associated with DART-MS is extremely rapid and samples are processed instantaneously, without the need for extraction, sample preparation, or other means that might compromise forensic evidence for future analyses. RESULTS: In a single assay, we demonstrated the ability to identify lubricant formulations associated with sexual assault, such as the spermicide nonoxynol-9, compounds used in condom manufacture, and numerous other trace components as probative evidence. In addition, the method can also serve to identify compounds within trace biological residues, such as fatty acids commonly identified in latent fingerprints. CONCLUSIONS: Characterization of lubricant residues as probative evidence serves to establish a connection between the victim and the perpetrator, and the availability of these details may lead to higher rates of prosecution and conviction, as well as more severe penalties. The methodology described here opens the way for the adoption of a comprehensive, rapid, and sensitive analysis for use in crime labs, while providing knowledge that can inform and guide criminal justice policy and practice.

A novel matrix-assisted laser desorption/ionisation mass spectrometry imaging based methodology for the identification of sexual assault suspects.

An increase in the use of condoms by sexual offenders has been observed. This is likely to be due both to the risk of sexually transmitted diseases and to prevent the transfer of DNA evidence. In this scenario the detection of condom lubricants at a crime scene could aid in proving corpus delicti. Here we show a novel application of Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry Imaging (MALDI MSI) for mapping the fingermark ridge pattern simultaneously to the detection of the condom lubricant within the fingermark itself. Two condom brands have been investigated to prove the concept. Condoms were handled producing lubricant-contaminated fingermarks. Images of the ridge pattern were obtained simultaneously to the detection of two lubricants, even several weeks after the fingermark deposition. The results therefore show the potential of MALDI MSI to link the suspect (identification through fingermark ridge pattern) to the crime (detection of condom lubricant) in one analysis. This would enable forensic scientists to provide evidence with stronger support in alleged cases of sexual assault.

Highly Soluble Drugs Directly Granulated by Water Dispersions of Insoluble Eudragit® Polymers as a Part of Hypromellose K100M Matrix Systems.

The aim of the present study was to investigate the suitability of insoluble Eudragit® water dispersions (NE, NM, RL, and RS) for direct high-shear granulation of very soluble levetiracetam in order to decrease its burst effect from HPMC K100M matrices. The process characteristics, ss-NMR analysis, in vitro dissolution behavior, drug release mechanism and kinetics, texture profile analysis of the gel layer, and PCA analysis were explored. An application of water dispersions directly on levetiracetam was feasible only in a multistep process. All prepared formulations exhibited a 12-hour sustained release profile characterized by a reduced burst effect in a concentration-dependent manner. No effect on swelling extent of HPMC K100M was observed in the presence of Eudragit®. Contrary, higher rigidity of formed gel layer was observed using combination of HPMC and Eudragit®. Not only the type and concentration of Eudragit®, but also the presence of the surfactant in water dispersions played a key role in the dissolution characteristics. The dissolution profile close to zero-order kinetic was achieved from the sample containing levetiracetam directly granulated by the water dispersion of Eudragit® NE (5% of solid polymer per tablet) with a relatively high amount of surfactant nonoxynol 100 (1.5%). The initial burst release of drug was reduced to 8.04% in 30 min (a 64.2% decrease) while the total amount of the released drug was retained (97.02%).

Cloud-point preconcentration and spectrophotometric determination of trace amounts of molybdenum(VI) in steels and water samples.

A cloud-point extraction process using micelle of the cationic surfactant CTAB to extract Mo(VI) from aqueous solutions was investigated. The method is based on the color reaction of molybdenum with bromopyrogallol red in the presence of potassium iodide at pH 1.0 glycine/HCl buffer media and micelle-mediated extraction of complex. The optimal extraction and reaction conditions (e.g., surfactant concentration, reagent concentration and effect of time) were studied and the analytical characteristics of the method (e.g., limit of detection, linear range, preconcentration and improvement factors) were obtained. Linearity was obeyed in the range of 0.3-320.0 ng mL(-1) of molybdenum(VI) ion and the detection limit of the method was 0.1 ng mL(-1). The relative standard deviation (R.S.D.) and relative error for five replicate measurements of 65.0 ng mL(-1) Mo(VI) were 1.1% and 1.9%, respectively. The interference effect of some anions and cations was also tested. The method was applied to the determination of molybdenum(VI) in steels and tap water and well water samples.

Update on nonoxynol-9 as vaginal spermicide.

Nonoxynol-9 (N-9) is a typical surfactant. For more than 30 years that very property of N-9 has been successfully exploited for its spermicidal action. It is available as an over-the-counter, locally acting vaginal spermicide. The suitability of N-9 as a spermicide is elaborated in this article. The reasons why N-9 may fail as a contraceptive are discussed. In spite of many drawbacks, which are mentioned in the article, N-9 is still often resorted to as a locally acting contraceptive. The review ends with suggestions to alter the molecular structure of N-9 and to adjust the dosages.

Distribution and dissipation pathways of nonylphenol polyethoxylates in the Yellow River: Site investigation and lab-scale studies.

Spatial distribution of nonylphenol polyethoxylates (NPEOs) and nonylphenol (NP) was investigated in a field study in Lanzhou Reach of the Yellow River. NPEOs and their metabolites were found in the river, with the maximum dissolved concentrations of 6.38 nmol/L for NPEOs, 0.19 nmol/L for nonylphenol ethoxy acetic acids (NPECs) and 0.79 nmol/L for NP, respectively. The maximum concentrations in the sediment and suspended particle samples were 1.50 and 5.09 nmol/g for NPEOs and NP, respectively. The effects of particles, light and microorganism on the dissipation of NPEOs in the river water were investigated based on lab-scale experiments. When natural particles were removed, 72% and 22% degradation of NPEOs were achieved at 120 h in non-sterile and sterile conditions with light, respectively. Different concentrations of NPECs were also observed in these experiments. When suspended particle matters (SPMs) were present, about 38-50% of NPEOs were sorbed to the particulate phase in only 1 h. As a result, the degradation of NPEOs and production of NPECs were inhibited. However, the combined sorption and degradation in the presence of SPMs resulted in lower dissolved NPEO concentrations than those in the absence of SPMs. Biodegradation was the most important pathway for NPEOs degradation in the river water, while NPECs seemed to be produced through both biological and abiological pathways.

Tracking of the physical ageing of amorphous pharmaceutical polymeric excipients by positron annihilation spectroscopy.

The structural changes observed in several amorphous polymers, commonly applied in the pharmaceutical technology to ensure conventional or controlled drug release, during relatively short storage periods are illustrated. The results suggest that the apparent structure formation of polymer molecules with water and, possibly, with other additives plays a significant role in the formation of such important physical and chemical parameters of tablets as drug release rate and solubility. Positron annihilation lifetime spectroscopy (PALS) was used to detect the changes of the free volume in the studied polymers under different storage conditions. Positrons react to the structural changes of amorphous polymers very sensitively, so the method can be recommended as useful means for stability tests during the development phase of dosage forms containing such excipients.

Sorption of small metabolites of nonylphenol polyethoxylates in single and complex systems on aquatic suspended particulate matter.

Sorption of nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) as well as their binary and ternary mixtures were studied and compared on three simulated suspended particulate matters (SPMs). Sorption dynamics of NP on the three SPMs could be divided into two phases, the rapid sorption phase and the slow sorption phase. A third phase, 'apparent desorption' occurred before the slow sorption phase for NP1EO and NP2EO as well as for all mixtures. Initial sorption rate increased with the OC% content of the SPMs. At low concentration, the sorption of NP, NP1EO and NP2EO (only at low concentration for 3# SPM) followed linear isotherm on the three SPMs. The linear Kd value of NP or NP1EO increased with the OC% content of SPM. In mixtures, sorption of NP, NP1EO and NP2EO increased significantly, and a 'critical point', after which sorption increased significantly, was observed in certain sorption isotherms.

Efficacy of Bacillus thuringiensis against Phyllocnistis citrella (Lepidoptera: Phyllocnistidae).

The purpose of this work was to analyze the efficacy of Bacillus thuringiensis Berliner on the control of Phyllocnistis citrella Stainton (Lepidoptera: Phyllocnistidae) in laboratory and field trials. In the laboratory, four B. thuringiensis were used: Dipel (commercial formulation) tested at the concentrations of 25 x 10(6) and 25 x 10(8) spores/ml and the isolates K, 6, and 15 (collections of the University of Azores) at the concentration of 25 x 10(6) spores/ ml. A surfactant solution of nonoxinol also was tested with or without the different suspensions of B. thuringiensis. Leaves of Citrus sinensis (L.) Osbeck with second or third instars of leafminer larvae were used in all tests. Bacterial suspensions were applied topically on the surface of intact leaf mines or by injection inside the mine, near the head of the leafminer. When injecting both concentrations of Dipel into the mines, mortality of the leafminers increased compared with the topical application, although no significant differences were observed. The addition of the nonoxinol to the Dipel suspension, applied topically, increased the effect of B. thuringiensis, but differences were not significant. The mortality of the leafminers treated only with the nonoxinol solution increased significantly 48 h after treatment, compared with the control group, suggesting an insecticidal effect of this surfactant when used at a concentration of 0.01%. All the tested B. thuringiensis were equally active against the leafminer, either when applied topically or by mine injection. Field trials showed a significant difference between larval mortality of the control group and the results observed at the trees treated with B. thuringiensis 48 h after treatments.

The effects of nonyl phenoxypolyethoxyl ethanol on cell damage pathway gene expression in SK-NSH cells.

BACKGROUND/AIMS: Most pesticide formulations contain both chief and additive ingredients. But, the additives may not have been tested as thoroughly as the chief ingredients. The surfactant, nonyl phenoxypolyethoxylethanol (NP40), is an additive frequently present in pesticide formulations. We investigated the effects of NP40 and other constituents of a validamycin pesticide formulation on cell viability and on the expression of genes involved in cell damage pathways. METHODS: The effects of validamycin pesticide ingredients on cell viability and of NP40 on the mRNA expression of 80 genes involved in nine key cellular pathways were examined in the human neuroblastoma SK-N-SH cell line. RESULTS: The chemicals present in the validamycin pesticide formulation were cytotoxic to SK-N-SH cells and NP40 showed the greatest cytotoxicity. A range of gene expression changes were identified, with both up- and down-regulation of genes within the same pathway. However, all genes tested in the necrosis signaling pathway were down-regulated and all genes tested in the cell cycle checkpoint/arrest pathway were up-regulated. The median fold-change in gene expression was significantly higher in the cell cycle checkpoint/arrest pathway than in the hypoxia pathway category (p = 0.0064). The 70 kDa heat shock protein 4 gene, within the heat shock protein/unfolded protein response category, showed the highest individual increase in expression (26.1-fold). CONCLUSIONS: NP40 appeared to be particularly harmful, inducing gene expression changes that indicated genotoxicity, activation of the cell death (necrosis signaling) pathway, and induction of the 70 kDa heat shock protein 4 gene.

Assessment of new formulations of nonoxynol-9 coprecipitated with polyvinylpyrrolidone and iodine as possible vaginal contraceptives.

OBJECTIVE: To assess the in vitro spermicidal activity of new formulations of nonoxynol-9, coprecipitated with polyvinylpyrrolidone (PVP) or iodinated PVP, against human spermatozoa via the use of the Sander-Cramer test and the cervical mucus penetration test. DESIGN: Solutions of PVP-nonoxynol-9 and iodinated PVP-nonoxynol-9 containing nonoxynol-9 whole molecule (oligomers 1 to 18) and its isolated fractions (oligomers 8 to 10, 4 to 6, and 1 to 3) at various concentrations (microgram/mL) were prepared via serial dilutions. Spermicidal solutions were mixed with human semen to determine the minimal lethal dose (microgram/mL). In the Sander-Cramer test, the lethal dose was reported as the minimal dose capable of killing spermatozoa within 20 seconds. In the cervical mucus penetration test, the lethal dose was reported as the minimal dose capable of preventing penetration of spermatozoa into cervical mucus beyond the second millimeter length of the capillary. SETTING: Andrology laboratory, University of Kentucky, Lexington, Kentucky. PATIENT(S): Normospermic male donors. MAIN OUTCOME MEASURE(S): Spermicidal lethal dose determination of various nonoxynol-9 preparations containing the whole nonoxynol-9 molecule and its isolated fractions coprecipitated with PVP or iodinated PVP. RESULT(S): The use of PVP increased the aqueous solubility of the nonoxynol-9 formulations containing oligomers 1 to 18 and 8 to 10 slightly. The coprecipitation of the nonoxynol-9 formulations containing nonoxynol-9 oligomers 4 to 6 and 1 to 3 with PVP significantly increased their solubilization and spermicidal action in vitro. Moreover, the incorporation of iodine significantly decreased the minimal nonoxynol-9 dose required for complete killing of spermatozoa in preparations containing nonoxynol-9 oligomers 4 to 6 and 1 to 3. CONCLUSION(S): Incorporation of all three components tested in this study (PVP, nonoxynol-9, and iodine) enhanced the efficiency of the spermicidal preparations, especially for nonoxynol-9 preparations containing nonoxynol-9 oligomers 4 to 6 and 1 to 3.

Estimation of partitioning parameters of nonionic surfactants using calculated descriptors of molecular size, polarity, and hydrogen bonding.

A study was carried out to verify the capacity of the Abraham's solute descriptors (R2, an excess molar refraction; pi 2H, the dipolarity/polarizability; sigma alpha 2H and sigma beta 2H, the summation hydrogen-bond acidity and basicity; and Vx, the characteristic volume of McGowan) to predict the alkane-water partition coefficient (log Palk) of nonionic surfactants. Log P values were taken from the literature and examined for linear solvation energy-related (LSER) equations with calculated physicochemical descriptors. A stepwise multiple linear regression (MLR) analysis allowed us to derive LSER models which, unlike those previously published for a standard set of solutes, revealed that R2 and sigma beta 2H are the major contributors to log Palk. A minor contribution of Vx was also detected, whereas surprisingly sigma alpha 2H required a positive coefficient. The less relevant size effect seems to indicate that for nonionic surfactants the energy needed for creating a water cavity is largely compensated for by the favorable interactions of ethoxy groups in the polar chain with water, whereas the log P-increasing effect of hydrogen-bond donor groups could be explained by considering the occurrence of folded, more lipophilic conformers, favored by the formation of intramolecular hydrogen bonds in the apolar phase. This hypothesis was substantiated by the calculation of the molecular lipophilicity potential on the water-accessible surface of extended and folded conformers of two representative surfactants, selected by high-temperature molecular dynamics. Besides MLR, a principal component analysis on a larger set of descriptors, comprising three solubility parameters (delta D, based on dispersion forces; delta H, including the contribution of hydrogen bonding; delta O, overall solubility parameter) afforded the so-called principal properties, which were able to characterize nonionic surfactants and to satisfactorily assess their lipophilicity-related properties.

Synthesis and spermicidal activity of a putative nitric oxide-releasing derivative of nonoxynol-9.

OBJECTIVES: We report on the synthesis of a potential nitric oxide releasing derivative of nonoxynol-9 (N9). METHODS: This derivative was synthesised via AgNO3 mediated nitroxylation of a chloride derivative of a N9 which itself was synthesised by thionyl chloride mediated chlorination of N9. In an initial in vitro study the spermicidal efficacy of the nitric oxide derivative and the parent compound (N9) was examined using boar spermatozoa. Sperm motility and viability were examined. RESULTS: The data showed that nitroxylation of N9 did not disrupt spermicidal activity; both sperm motility and viability were comparable between N9 and its nitroxylated derivative. For both compounds, low doses (1-10 microg/mL) were sufficient to induce significant immobilization of sperm after 1 min, whereas concentrations of 10-100 microg/mL were required to achieve significant increase in membrane permeability. CONCLUSION: The results show that a nitric oxide-releasing derivative of N9 retains the spermicidal activity of the parent compound and may have other beneficial effects associated with the release of NO.

Comparative spermicidal performance of iodinated and non-iodinated contraceptive formulations of nonoxynol-9 co-precipitated with polyvinylpyrrolidone.

The objective of this study was to evaluate the spermicidal qualities of various combinations of nonoxynol-9 (N-9; whole molecule = oligomers 1-18) and its isolated fractions (oligomers 8-10, 4-6 and 1-3), co-precipitated with non-iodinated and/or iodinated (Io) polyvinylpyrrolidone (PVP) as possible vaginal contraceptives. Spermicidal qualities of known equimolar concentrations of various combinations of PVP/N-9 and PVP-Io/N-9 were tested via a modified Sander-Cramer test (SCT) using human spermatozoa. Spermicidal agents and semen samples were mixed 1:1 (v/v) and evaluated for sperm viability. Spermicidal activity was reported as the minimal concentration (microgram/mL) of spermicide capable of killing all spermatozoa within 20 sec after exposure to the spermicide. The spermicidal activity of PVP/N-9 and PVP-Io/N-9 preparations containing N-9 oligomers 1-18 and/or 8-10 was similar, and these preparations were more efficient in killing the spermatozoa than the ones containing N-9 oligomers 4-6 and 1-3. Polyvinyl-pyrrolidone proved to be an effective vehicle for PVP/N-9 and PVP-Io/N-9 preparations, especially those containing N-9 oligomers 4-6 and 1-3. Incorporation of Io into the spermicidal preparations brought about additional efficacy. The current findings could be of clinical significance in future studies when preparing and delivering those selected co-precipitates vaginally.

PIP: At the University of Kentucky in Lexington, pooled normospermic semen specimens collected after 3-4 days of sexual abstinence were co-precipitated with non-iodinated and/or iodinated (Io) polyvinylpyrrolidone (PVP) to determine the spermicidal qualities of various combinations of nonoxynol-9 (N-9) (oligomers 1-18) and its isolated fractions (oligomers 8-10, 4-6, and 1-3) as possible vaginal contraceptives. The Sander-Cramer test on human spermatozoa was used to test the spermicidal qualities of known equimolar concentrations of various combinations of PVP/N-9 and PVP-Io/N-9. The minimal lethal dose (LD) concentration (mcg/ml) of spermicide capable of killing all spermatozoa within 20 seconds after exposure to the spermicide was the definition of spermicidal activity. The LD of PVP/N-9 and PVP-Io/N-9 spermicidal preparations containing N-9 oligomers 1-18 and/or 8-10 was similar (165-166/mcg/ml for PVP/N-9 and 193-231/mcg/ml for PVP-Io/N-9). These particular preparations were more efficient in destroying spermatozoa than those containing N-9 oligomers 4-6 and 1-3 (p 0.05). PVP appeared to an efficient vehicle for the studied spermicides, particularly those containing N-9 oligomers 4-6 and 1-3. The addition of Io into PVP/N-9 preparations improved spermicidal activity, and significantly so, for N-9 oligomers 4-6 and 1-3 (495 mcg/ml for non-iodinated PVP/N-9 vs. 385 mcg/ml for PVP-Io/N-9; p 0.05). These findings will help future studies when the researchers prepare and deliver spermicides that co-precipitate vaginally.

Study of crystallization of endogenous surfactant in Eudragit NE30D-free films and its influence on drug-release properties of controlled-release diphenhydramine HCl pellets coated with Eudragit NE30D.

This study investigates the crystallization of the endogenous surfactant nonoxynol 100 in Eudragit NE30D-free films during storage and the influences of nonoxynol 100 on the dissolution of diphenhydramine hydrochloric acid (HCl) pellets coated with Eudragit NE30D before and after aging at ambient conditions. Polarizing light microscopy showed that when Eudragit NE30D-free films were stored at ambient conditions, off-white, flower-shaped crystals formed and increased in the polymer film as storage time increased. Also, x-ray diffraction showed polymer crystals in the aged free film. Thermogravimetric analysis showed no evidence of combined volatile molecules with the polymer molecules, and Fourier transformed infrared spectroscopy (FTIR) data suggested the same chemical composition of the polymer before and after phase separation. Further, from normal light microscopy, the appearance of the melting droplets in the polymer film indicated that the polymer molecules did not form the crystals. After the extraction of nonoxynol 100 by water, the free film formed by the water-extracted Eudragit NE30D was found free of the crystals after aging at the same conditions. The combination of the thermogravimetric analysis, FTIR, and microscopy showed that the origin of the crystals in dry Eudragit NE30D-free films came from nonoxynol 100, and not from the polymer molecules themselves. Monitoring by differential scanning calorimeter, it was found that the rates of crystallization of nonoxynol 100 were faster when the films were stored at 30 degrees C and 40 degrees C than when stored at ambient conditions and 45 degrees C. When stored at -5 degrees C, the crystallization rate was nearly zero. As the temperature got closer to melting temperature, the crystallization rate was very low because the system was in a thermodynamically disfavored state. The rate gradually increased and finally passed through a maximum as the crystallization temperature decreased. As the temperature kept decreasing, the crystallization rate became small again and eventually stopped because the system turned into a kinetically disfavored state. Because the phase transition of nonoxynol 100 in Eudragit NE30D occurred at ambient conditions, its influence on the dissolution of diphenhydramine HCl pellets coated with Eudragit NE30D was studied. Three different levels of nonoxynol 100 were used in Eudragit NE30D dispersions to make 3 different batches of Eudragit NE30D film-coated, controlled-release diphenhydramine HCl pellets. The results showed the dissolution rate increased as the level of nonoxynol 100 increased in the coating formula. Compared to the commonly used water-soluble additive human peripheral mononuclear cell, nonoxynol 100 was more effective in enhancing the dissolution of diphenhydramine HCl from pellets coated with Eudragit NE30D. Further study showed that the phase separation of the surfactant during aging tends to stabilize or slightly increase dissolution rates at higher surfactant levels.

A case study on forensic polymer analysis by DIOS-MS: the suspect who gave us the SLIP.

New technology was used to identify traces of a commercial barrier/spermicide in evidence from a case of a man accused of rape of a minor. Examination of vaginal swabs performed by another laboratory had been negative for seminal fluid or other sources of DNA from the suspect and we were asked to examine the remaining swabs for any traces that might have originated from the commercial product. Encare consists of vaginal inserts having a suppository-like shape. They contain the spermicide, nonoxynol-9, in a matrix consisting of approximately two parts polyethylene glycol (PEG) 1000 to one part PEG 1450, plus minor inorganic components added to produce foaming. Portions of the cotton from vaginal swabs from the victim and penile swabs from the suspect were extracted with methanol and subsequently examined by desorption ionization on silicon time-of-flight mass spectrometry (DIOS TOF MS). Low levels of PEG in the same mass range as Encare were found on two separate vaginal swabs from the victim and one penile swab from the suspect. Subsequent to these findings, the suspect (through his attorneys) provided us with a sample of SLIP Plus, a commercial sexual lubricant that also contains nonoxynol-9. Traces of PEG in the same mass range as Encare were found in this sample, while no PEG was found in a sealed sample of SLIP Plus provided by the manufacturer. At trial the suspect's attorneys stipulated that their client had added some Encare to the SLIP Plus sample he had provided.

Electrospray and MALDI mass spectrometry in the identification of spermicides in criminal investigations.

Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry have been used to examine evidence in a sexual assault investigation. Because condoms are being used increasingly by sexual assailants and some condom brands include the spermicide nonoxynol-9 (nonylphenoxy polyethoxyethanol) in the lubricant formulation, the recovery, and identification of nonoxynol-9 from evidence items may assist in proving corpus delicti. A method was developed for the recovery of nonoxynol-9 from internal vaginal swabs and for its identification by reverse phase liquid chromatography/electrospray ionization mass spectrometry (LC ESI-MS), nanoelectrospray ionization (nanoESI) mass spectrometry, and high resolution MALDI Fourier transform mass spectrometry (MALDI-FTMS). The method was tested on extracts from precoitus, immediate postcoitus, and four-hours postcoitus vaginal swabs provided by a volunteer whose partner does not normally use condoms, but for this trial used a condom having a water-soluble gel-type lubricant that includes 5% nonoxynol-9 in its formulation. Subsequently, LC ESI-MS was used to identify traces of nonoxynol-9 from the internal vaginal swab of a victim of a sexual assault.

Coprecipitation of nonoxynol-9 with polyvinylpyrrolidone to decrease vaginal irritation potential while maintaining spermicidal potency.

The aim of this study was to test the hypothesis that polyvinylpyrrolidone (PVP) would increase the critical micelle concentration (CMC) of nonoxynol-9 (N-9), providing a reduction in its irritation potential, while maintaining essential spermicidal activity. Solid coprecipitates of N-9 with PVP were manufactured with the use of a modified lyophilization process. The irritation potential of N-9 was estimated by an in vitro assay, monitoring the extent of hemolysis of red blood cells. CMCs of N-9 were measured in the presence of various concentrations of PVP. A modified Sander-Cramer assay was implemented to measure the spermicidal activity of N-9 and the N-9/PVP coprecipitates. With the use of the lyophilization process and more suitable solvents, solid coprecipitates of N-9/PVP were manufactured with no residual organic solvents. The irritation potential of N-9 was reduced when in the presence of PVP-50% hemolysis values increased from 0.054 mM to more than 0.2mM. N-9 CMC values increased in the presence of PVP from 0.085 mM (0% PVP) to 0.110 mM (3.5% PVP) and 0.16 6mM (10% PVP). However, spermicidal activities ranged from 0.213 mM to 0.238 mM, N-9 remaining steady regardless of the amount of PVP. By use of N-9/PVP coprecipitates, the self-association properties and irritation potentials of N-9 were altered. This result suggests a process to produce a spermicidal product that reduces the detrimental implications to the vaginal epithelium while maintaining the essential spermicidal activity.

Sorption of biodegradation end products of nonylphenol polyethoxylates onto activated sludge.

Nonylphenol(NP), nonylphenoxy acetic acid (NP1EC), nonylphenol monoethoxy acetic acid (NP2EC), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) are biodegradation end products (BEPs) of nonionic surfactant nonylphenolpolyethoxylates (NPnEO). In this research, sorption of these compounds onto model activated sludge was characterized. Sorption equilibrium experiments showed that NP, NP1EO and NP2EO reached equilibrium in about 12 h, while equilibrium of NP1EC and NP2EC were reached earlier, in about 4 h. In sorption isotherm experiments, obtained equilibrium data at 28 degrees C fitted well to Freundlich sorption model for all investigated compounds. For NP1EC, in addition to Freundlich, equilibrium data also fitted well to Langmuir model. Linear sorption model was also tried, and equilibrium data of all NP, NP1EO, NP2EO and NP2EC except NP1EC fitted well to this model. Calculated Freundlich coefficient (K(F)) and linear sorption coefficient (K(D)) showed that sorption capacity of the investigated compounds were in order NP > NP2EO > NP1EO > NP1EC approximately NP2EC. For NP, NP1EO and NP2EO, high values of calculated K(F) and K(D) indicated an easy uptake of these compounds from aqueous phase onto activated sludge. Whereas, NP1EC and NP2EC with low values of K(F) and K(D) absorbed weakly to activated sludge and tended to preferably remain in aqueous phase.