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Widening the methodology of chromophore analysis in pulp and paper science, a sensitive gas-chromatographic approach with electron-capture detection is presented and applied to model samples and real-world historic paper material. Trifluoroacetic anhydride was used for derivatization of the chromophore target compounds. The derivative formation was confirmed by NMR and accurate mass analysis. The method successfully detects and quantifies hydroxyquinones which are key chromophores in cellulosic matrices. The analytical figures of merit appeared to be in an acceptable range with an LOD down to approx. 60 ng/g for each key chromophore, which allows for their successful detection in historic sample material. [ABSTRACT FROM AUTHOR]

[Display omitted] • A high SERS efficiency Au nanodendrite (AuND) structure was constructed by electro-deposition on a 3D nickel foam (NiF). • NiF with a highly porous structure and concave microchannel was employed as a sampling-diffusing medium. • AuND/NiF was situated onto a paper strip to construct a paper-based chromatography device (PP-AuND/NiF). • AuND/NiF substrate could detect R6G at 0.1 nM. • The PP-AuND/NiF could simultaneously separate and detect R6G in a mixture solution containing R6G and 2-NpSH. A simple paper-based chromatography coupling with nickel foam decorated Au nanodendrite (PP-AuND/NiF) was fabricated for simultaneous separation and surface-enhanced Raman scattering (SERS) detection of Rhodamine-6G (R6G) from a mixture of analytes. The three-dimensional porous nickel foam (NiF) was employed as a sampling diffusion platform, and AuND with a high surface active area beneficial for SERS efficiency was electro-deposited directly onto the NiF frame. The structure of AuND/NiF was characterized by X-ray diffraction and scanning electron microscopy. The AuND/NiF could detect R6G at 0.1 nM, and the enhancement factor was 1.84 x 106. The AuND/NiF was durable, with a slight signal decrease after 6 m of drop-testing. Also, upon three days of exposure to ambient air, the signal droped only 3.35 %. Subsequently, the PP-AuND/NiF was constructed by directly situating AuND/NiF on a paper strip, serving as a sample in and out to AuND/NiF. A mixture of two SERS active compounds, namely 2-Naphthalenethiol (2-NpSH) and Rhodamine 6G (R6G), was prepared in ethanol: water (1:1) solution to evaluate PP-AuND/NiF separation capability. Raman measurements along different distances of AuND/NiF were performed, and the signal of 2-NpSH was dismissed after 3.0 mm, while R6G's signals were observed throughout AuND/NiF. In general, the PP-AuND/NiF demonstrated effective separation and SERS measurement of analytes in a mixture, which could be applicable for more complex samples in the future, especially in clinical analysis. [ABSTRACT FROM AUTHOR]

In this study we investigated the underlying mechanisms of coffee stain formation on paper – a porous substrate. When a drop of aqueous liquid containing dispersed materials dries on paper, the faster water evaporation rate at the edge of the drop drives the redistribution of the dispersed materials to the edge of the drop-covered area on paper. Deegan׳s discovery has been accepted as the “coffee ring” phenomenon, which has wide implications. However, stains left by dried aqueous liquids on paper are not always ring-shaped. This is because, besides Deegan׳s coffee ring effect, the transport of dispersed materials in porous media is affected by chromatographic and filtration effects, which are highly dependent upon the properties of the substrates. In this work we clarify the influences of different mechanisms to the dispersed materials redistribution in paper. [ABSTRACT FROM AUTHOR]

Abstract: A quick and direct method for identifying organic components of papers in library and archival collections with minimal destructive sampling is needed for preservation, forensic, and general purposes. Direct analysis in real time mass spectrometry (DART-MS) is used for characterizing 16 reference papers of known manufacture in terms of their pulp composition and pitch contaminants. Unique mass spectra are obtained from bleached kraft, chemithermomechanical, and stone groundwood pulp papers in real time without extractions, derivatizations, chromatographic separations, and other time- and chemical-consuming sample preparations. Phytosteroids are volatilized from bleached hardwood kraft but not from bleached softwood kraft papers, which differentiates the two of them. The kraft papers are in turn differentiated from chemithermomechanical pulp papers by lignin-derived thermolyis products: syringyl products arise from hardwood, but guaiacyl and coumaryl products arise from softwood, chemithermomechanical pulp papers. Stone groundwood papers contain a number of extractives that are volatilized, which serve to differentiate them from all the other papers. Papers that contain rosin vs. alkyl ketene dimer (AKD) sizings are immediately differentiated. The DART-MS methodology is fast and simple, and the spectra are repeatable. Microsamples as small as ∼10μg tweezed from the paper surface may be analyzed. These benchmark spectra are the prelude to further applications of DART-MS in paper research and the beginning of the development of a searchable library of DART-MS spectra of printing and writing papers by the Library of Congress. [Copyright &y& Elsevier]

Abstract: The efficiency of several lab scale treatments (aerobic, anaerobic and ozone or combination of these) was evaluated using two packaging board mill whitewaters. The effect of the different treatments on the elimination of the organic load, the chemical oxygen demand (COD) and the toxicity was tested as well as the relationship between these parameters. Biocides, phenolic compounds, surfactants, plasticiziers and wood extractives were identified in untreated and treated whitewaters by liquid chromatography coupled with mass spectrometry (LC–MS) or gas chromatography coupled with mass spectrometry (GC–MS). A strong dependency on the water type and treatment efficiency was observed, being the combination of anaerobic and aerobic treatments the best option to reduce the organic contaminants in these waters, although in some cases, the toxicity did not decrease. However, ozone as post-treatment permitted a further reduction of organic compounds, toxicity and COD. [Copyright &y& Elsevier]

Highlights: [•] Improvement of the direct quantification with analytical pyrolysis. [•] Optimization of the chromatographic parameters after pyrolysis of cationic starch. [•] Quantification of cationic starches in cellulose matrixes. [•] Validation of the cationic starch quantification in paper samples. [ABSTRACT FROM AUTHOR]

Abstract: A simple and sensitive high performance liquid chromatographic (HPLC) method with UV detection was developed for the determination of new diethanolamine derivative complexing agents. The quantitation of three complexing agents was accomplished as their Cu(II) complexes and their separation on a reversed phase C18 column using 0.01M tetrabutyl ammoniumhydroxide and methanol as isocratic mobile phase. The limit of detection (LOD) ranges from 0.1 to 2.0mg/l and the method has a wide linear range, from LOD to 150mg/l. The method was successfully applied for the analysis of lake water and wastewater effluent from pulp and paper mill spiked with studied complexing agents. [Copyright &y& Elsevier]

Abstract: Iron gall inks were the most often used inks from the Middle Ages until the 20th century; examples include the drawings by Leonardo and scores by Bach. These masterpieces are threatened by the corrosive properties of the ink. In order to increase the longevity of the materials, stabilisation treatments have been developed during the last two decades. Their effectiveness has often been determined by comparing rates of degradation during accelerated tests. However, such evaluation using historical materials is limited by the amount of material required by various analytical methodologies. The paper describes the use of size exclusion chromatography (SEC) of cellulose containing iron gall ink, derivatised using phenyl isocyanate. A linear correlation is observed between the weight average degree of polymerisation obtained with SEC and the one obtained using viscometry, with a slope of 1.4. The method was used to evaluate the extent of stabilisation of historic documents containing iron gall inks during accelerated degradation. Despite considerable uncertainty, also caused by the heterogeneity of historic materials, it is demonstrated that efficient stabilisation by factors of 10 and 20 times is achievable using a calcium phytate treatment. [Copyright &y& Elsevier]

Abstract This paper describes the development of two microfluidic paper-based analytical devices (μPADs), one well-based and the other based on a lateral flow assay (LFA) configuration, to detect glucose via a colorimetric assay using the solid metal-organic framework (MOF) Zr-PCN-222(Fe), to encapsulate glucose oxidase (GOx). The well-based platform consisted of laminate sheets and multiple layers of wax-printed chromatography paper. Solutions of KI and glucose placed into the well flowed through the device and reacted with the GOx@MOF species sandwiched between the paper layers realizing a yellow-brown color. The LFA platform consisted of chromatography paper between parafilm and polyvinyl acetate (PVA) layers. GOx@MOFs spotted on the paper subjected to solutions of KI and glucose yielded a brown color. The devices were then dried, scanned, and analyzed yielding a correlation between average inverse yellow intensity and glucose concentrations. The development of these devices employing MOFs as biomimetic catalysts should further expand the applications of microfluidic technologies for sensors a variety of analytes. Graphical abstract Image 1 Highlights • Paper-based microfluidic devices employing a metal-organic framework detect glucose. • Metal-organic frameworks are effective encapsulating species for enzymes. • Sensors constructed from paper are easy to fabricate and are low-cost. [ABSTRACT FROM AUTHOR]

• Recent advances in paper/thread-based zone and capillary electrophoresis techniques. • Various sample pretreatment methods using electrophoresis on wicking substrates. • Review of unmodified and modified microfluidic paper/threat -based chromatography. • Application of paper/threat -based chromatography in blood separation. Paper and thread are widely used as the substrates for fabricating low-cost, disposable, and portable microfluidic analytical devices used in clinical, environmental, and food safety monitoring. Concerning separation methods including chromatography and electrophoresis, these substrates provide unique platforms for developing portable devices. This review focuses on summarizing recent research on the miniaturization of the separation techniques using paper and thread. Preconcentration, purification, desalination, and separation of various analytes are achievable using electrophoresis and chromatography methods integrated with modified or unmodified paper/thread wicking channels. A variety of 2D and 3D designs of paper/thread platforms for zone electrophoresis, capillary electrophoresis, and modified/unmodified chromatography are discussed with emphasis on their limitation and improvements. The current progress in the signal amplification strategies such as isoelectric focusing, isotachophoresis, ion concentration polarization, isoelectric focusing, and stacking methods in paper-based devices are reviewed. Different strategies for chromatographic separations based on paper/thread will be explained. The separation of target species from complex samples and their determination by integration with other analytical methods like spectroscopy and electrochemistry are well-listed. Furthermore, the innovations for plasma and cell separation from blood as an important human biofluid are presented, and the related paper/thread modification methods are explored. [ABSTRACT FROM AUTHOR]

Telomerase is extensively expressed in various cancer cells and recognized as a target for cancer drug discovery. In the present study, a simple and amplification-free fluorescence assay based on polyamidoamine starburst dendrimer (PAMAM dendrimer)-activated paper device is proposed for sensitive detection of telomerase activity through hybridization of Cy5 modified single strand DNA probes with telomerase extension products. The paper substrate is fabricated by hand drawing according to a template, which is low cost, instrument free and easy operation. PAMAM is rich in amino groups on its surface and employed to immobilize the telomerase substrate (TS) primer. Highly sensitive detection of telomerase activity in HeLa cell lysate of 10 cells is achieved since the PAMAM dendrimer-activated paper surface can provide high density of binding sites for immobilization of TS primer. The experimental results also demonstrate that the assay can be employed to evaluate telomerase activity levels of various cell lines and screen telomerase inhibitors. [ABSTRACT FROM AUTHOR]

Graphical abstract A colorimetric sensor MOESQ based on squaraine was synthesized to detect Cu2+ in CH 3 CN with the detection limit of 1.88 × 10−7 molL−1. By adsorbing MOESQ on the chromatography paper, a colorimetric test paper for Cu2+ was prepared, which could detect Cu2+ with the color change from blue to faint yellow in the limit of detection concentration of 10−6 molL−1. Highlights • N,N'-bis(2-methoxy-ethyl) squaraine with λ abs and λ em of 643 nm 653 nm in CH 3 CN. • A colorimetric squaraine probe for selective detection of Cu2+ ion in acetonitrile. • The squaraine-based test paper for rapidly and easily detecting Cu2+ by naked eyes. • Cu2+ detection limit 1.88 × 10−7 molL−1 in CH 3 CN and 10−6 molL−1 for the test paper. Abstract A colorimetric probe N,N'-bis(2-methoxy-ethyl)-2,3,3-trimethyl-3H-squaraine (MOESQ) with H 2 O solubility was synthesized to detect Cu2+. MOESQ exhibits good selectivity, high sensitivity and fast UV-Vis response toward Cu2+ over other competing ions in CH 3 CN. The detection limit of MOESQ for Cu2+ in CH 3 CN can reach 1.88 × 10−7 molL−1. By adsorbing MOESQ on the chromatography paper, a colorimetric test paper for Cu2+ was prepared, which could detect Cu2+ with the color change from blue to faint yellow even in the limit of detection concentration of 10−6 molL−1. [ABSTRACT FROM AUTHOR]

This paper describes a new approach for the massive production of electrochemical paper-based analytical devices (ePADs). These devices are fully fabricated by screen-printing technology and consist of a lineal microfluidic channel delimited by hydrophobic walls (patterned with diluted ultraviolet screen-printing ink in chromatographic paper grade 4) and a three-electrode system (printed with carbon and/or Ag/AgCl conductive inks). The printing process was characterised and optimized for pattern each layer with only one squeeze sweep. These ePADs were used as transducers to develop a glucose biosensor. Ionic strength/pH buffering salts, electrochemical mediator (ferricyanide) and enzyme (glucose dehydrogenase FAD-dependent) were separately stored along the microfluidic channel in order to be successively dissolved and mixed after the sample dropping at the entrance. The analyses required only 10 µl and the biosensors showed good reproducibility (RSD = 6.2%, n = 10) and sensitivity (0.426 C/M cm 2 ), wide linear range (0.5–50 mM; r 2 = 0.999) and low limit of detection (0.33 mM). Furthermore, the new biosensor was applied for glucose determination in five commercial soft-drinks without any sample treatment before the analysis. These samples were also analysed with a commercial enzymatic-kit assay. The results indicated that both methods provide accurate results. [ABSTRACT FROM AUTHOR]

This study presents the research on the chemical analysis and genotoxicity of 28 virgin/recycled paper products in food-contact use. In the chemical analysis, paper products were extracted by reflux with ethanol, and analyzed by gas chromatography/mass spectrometry. 4,4′-bis(dimethylamino)benzophenone (Michler''s ketone: MK), 4,4′-bis(diethylamino)benzophenone (DEAB), 4-(dimethylamino)benzophenone (DMAB) and bisphenol A (BPA) were found characteristically in recycled products. Seventy-five percent of the recycled paper products contained MK (1.7–12 μg/g), 67% contained DEAB (0.64–10 μ g/g), 33% contained DMAB (0.68–0.9 μg/g) and 67% contained BPA (0.19–26 μg/g). Although, BPA was also detected in virgin paper products, the detection levels in the recycled products were ten or more times higher than those in the virgin products. The genotoxicity of paper and paperboard extracts and compounds found in them were investigated by Rec-assay and comet assay. Of the 28 products tested by Rec-assay using Bacillus subtilis, 13 possessed DNA-damaging activity. More recycled than virgin products (75% against 25%) exhibited such activity, which, of the compounds, was observed in BPA, 1,2-benzisothiazoline-3-one (BIT), 2-(thiocyanomethylthio)benzothiazole, 2,4,5,6-tetrachloro-isophthalonitrile, 2,4,6-trichlorophenol (TCP), and pentachlorophenol. The critical toxicant in one virgin paper product was concluded to be BIT. Eight samples with DNA-damaging activity were also tested by comet assay using HL-60 cells; six induced comet cells significantly (five times or higher than the control) without a decrease of viable cells. TCP, BZ, DEAB, and BIT also caused a slight increase in comet cells. In conclusion, we showed that most recycled paper products contain chemicals such as MK, DEAB, DMAB, and BPA, and possess genotoxicity. However, the levels of the chemicals in the recycled products could not explain their genotoxic effects. [Copyright &y& Elsevier]

New psychoactive substances (NPS) have been associated with fatalities and severe injuries in a number of cases in the United States and have led investigators to rethink traditional drug monitoring protocols. Of particular interest are the variable phenethylamine chemical structures known as 'NBOMes', which pose an emerging threat to public health with incidence steadily growing over the past decade. In this study, direct sample analysis (DSA)-time of flight mass spectrometry was employed to leverage rapid and sensitive ambient ionization mass spectrometry without chromatographic separation as verified with an authentic case sample. Samples for method development were prepared at Boston University School of Medicine's Biomedical Forensic Sciences program (Boston, MA) and analyzed at the State of Maine Health and Environmental Testing Laboratory's Forensic Chemistry Section (Augusta, ME). Preliminary method development work was performed at the University of Central Florida (Orlando, FL). DSA without any extraction step in addition to the evaluation of methanol, dichloromethane and hexane extractions were conducted. Methanol was found to not be a suitable extraction solvent for DSA analysis of these compounds. For the screening of NBOMe designer drug variables on blotter paper, DSA-TOFMS was successful at reducing analysis time to ∼15s per sample, for qualitative identification for the selected analytes of interest. The analysis of an authentic forensic case sample by DSA-TOFMS using the method development parameters demonstrates its utility in forensic laboratories. 25C-NBOMe was identified with an exact mass accuracy of 0.60ppm. [ABSTRACT FROM AUTHOR]

The present work reports on the development of a pressure-affected based headspace (HS) analytical technique for the determination of calcium carbonate content in paper samples. By the acidification, the carbonate in the sample was converted to CO 2 and released into the headspace of a closed vial and then measured by gas chromatography (GC). When the amount of carbonate in the sample is significant, the pressure created by the CO 2 affects the accuracy of the method. However, the pressure also causes a change in the O 2 signal in the HS-GC measurement, which is a change that can be used as an indirect measure of the carbonate in the sample. The results show that the present method has a good precision (the relative standard deviation < 2.32%), and good accuracy (the relative differences compared to a reference method was < 5.76%). Coupled with the fact that the method is simple, rapid, and accurate, it is suitable for a variety of applications that call for the analysis of high carbonate content in paper samples. [ABSTRACT FROM AUTHOR]

We studied the aging behaviour of gelatin used to size paper. Thus far, research on the aging of paper has largely ignored the sizing agent. Degradation of the protein was characterised and the impact of paper components, such as cellulose, and aluminium potassium sulphate was evaluated. Whatman No. 1 filter papers sized with two types of gelatins (A and B) were prepared as model samples. Commercially sized modern papers (Arches) were also studied in order to compare laboratory samples with real artist papers. Both types of papers were artificially aged (80 °C, 50% relative humidity for 35 and 94 days). Historic papers were included in the study in order to compare artificially aged with naturally aged gelatin. The aqueous extracts from the papers were characterised by aqueous size-exclusion chromatography (SEC) using four PL-Aquagel-OH columns and UV photodiode array detection at 220, 254 and 280 nm. Results showed that gelatin undergoes hydrolysis upon aging, type A gelatin showing a faster degradation rate than type B. The result was an increase in the lower-molar-mass fractions, under 50 000 g mol−1, and especially in a characteristic fraction with a peak molecular mass (Mp) of 14 000 g mol−1. A significant decrease in the extraction yields of α-, β- and γ-chains occurred after aging. This was attributed to crosslinking, leading to the formation of less-soluble polypeptides with very high molar mass (>800 000 g mol−1). Less than 10% alum had no impact on the degradation rate; higher alum contents accelerated hydrolysis reactions. [Copyright &y& Elsevier]

This article details the study of electrochemical behavior of new carbon electrodes based on pyrolysis of different paper sources to be used in biosensor applications. The resistivity of the pyrolyzed papers was initially used as screening parameters to select the best three paper samples (imaging card paper, multipurpose printing paper, and 3MM chromatography paper) and assemble working electrodes that were further characterized by a combination of microscopy, electrochemistry, and spectroscopy. Although slight differences in performance were observed, all carbon substrates fabricated from pyrolysis of paper allowed the development of competitive biosensors for uric acid. The presented results demonstrate the potential of these electrodes for sensing applications and highlight the potential advantages of 3MM chromatography paper as a substrate to fabricate electrodes by pyrolysis. [ABSTRACT FROM AUTHOR]

Point-of-collection (POC) devices aim for a fast, on-site detection for medical and environmental purposes. In this area, microfluidic Paper-based Analytical Devices (μPADs) have recently gained popularity because these are potentially cheap and environmentally friendly to produce, and easy to use. From an analytical perspective, paper is well known for its use as a substrate for chromatography, but less known for its use in electrophoretic separations. With the recent interest in μPADs, most applications are based on rather simple assays with relatively few applications incorporating an analytical separation. The focus of this review is on paper-based electrophoresis, originating with the key developments in the 1940s and 1950s as well as the recent developments of electrophoretic μPADs, and concluding with a critical discussion of the opportunities and challenges for electrophoretic μPADS in the future. [ABSTRACT FROM AUTHOR]

Cachaça is the popular name of sugarcane liquor obtained from fermented sugarcane mash broth. This is one of the most popular alcoholic beverages in Brazil and is gaining ground in the global market. One of the quality parameters established by Brazilian law is the sum of the concentrations of furfural and hydroxymethylfurfural, two compounds that give the beverage an unpleasant taste and have mutagenic potential. These two substances are usually determined by chromatographic techniques that employ toxic organic solvents that can be damaging to the health of the operator and to the environment. This paper describes the development of a new methodology to determine furfural and hydroxymethylfurfural in sugarcane liquor using a diffuse reflectance technique coupled with limited-area spot-testing on a paper platform. The new method presented LOQ values of 0.74 mg L − 1 for furfural and 1.27 mg L − 1 for hydroxymethylfurfural. Recoveries in the ranges 89.5–108% (furfural) and 96.3–106% (hydroxymethylfurfural) indicated that there was no significant influence of the matrix in determination of the analytes. The method was applied using eleven sugarcane liquor samples from different locations in Brazil. [ABSTRACT FROM AUTHOR]

This paper presents a simple and low-cost method for patterning poly(dimethylsiloxane) (PDMS) barriers in porous support such as paper for the construction of flexible microfluidic paper-based analytical devices (μPADs). The fabrication method consisted of contact-printing a solution of PDMS and hexane (10:1.5 w/w) onto chromatographic paper using custom-designed rubber stamps containing the patterns of μPADs. After penetrating the paper (∼30 s), the PDMS is cured to form hydrophobic barriers. Under optimized conditions, hydrophobic barriers and hydrophilic channels with dimensions down to 949 ± 88 μm and 771 ± 90 μm ( n = 5), respectively, were obtained. This resolution is well-suitable for most applications in analytical chemistry. Chemical compatibility studies revealed that the PDMS barriers were able to contain some organic solvents, including acetonitrile and methanol, and aqueous solutions of some surfactants. This find is particularly interesting given that acetonitrile and methanol are the most used solvents in chromatographic separations, non-aqueous capillary electrophoresis and electroanalysis, as well as aqueous solutions of surfactants are suitable mediums for cell lyses assays. The utility of the technique was evaluated in the fabrication of paper-based electrochemical devices (PEDs) with pencil-drawn electrodes for experiments in static cyclic voltammetry and flow injection analysis (FIA) with amperometric detection, in both aqueous and organic mediums. [ABSTRACT FROM AUTHOR]

Abstract: Pyrolysis-gas chromatography (Py-GC) has been applied to the evaluation of the deteriorated acidic paper in old books. A tiny piece (ca. 0.25mg) of deteriorated paper was subjected to Py-GC measurement at 300°C pyrolysis temperature. Levoglucosan and its dehydrated form levoglucosenone were typical degradation products while a recent control paper gave rise mainly to levoglucosan. The relative yield of levoglucosenone was much higher for the paper sample taken at the heavily deteriorated marginal part than that in the center of the same page of the old book. Accordingly, levoglucosenone observed in the pyrogram can be used as a marker to evaluate the degree of the deterioration of the acidic paper. The formation of levoglucosenone can be attributed to the slow deterioration process of paper, in which dehydration reaction play an important roll accompanied by the chain scission of cellulose. The Py-GC method for paper evaluation was also applied to clarify the effect of storage conditions and chemical compositions of paper materials to their deterioration processes. [Copyright &y& Elsevier]

Although nucleic acid amplification test (NAT) is widely used for pathogen detection, rapid NAT systems that do not require special and expensive instruments must be developed in order to enable point of care (POC)-NATs, which contribute to early initiation of treatment. As a POC-NAT system, Kaneka DNA chromatography chip (KDCC), developed using DNA tag-bound primer through modified substance, was shown to be suitable for POC testing, due to the rapid detection time, simple procedures, and low manufacturing costs. However, owing to some modifications in primer, the detection performance and amplification speed were shown to be reduced when using KDCC, counteracting the increased speed of detection. To solve these issues and improve the speed of this NAT system, we investigated a better modification substance for KDCC. Here, azobenzene-modified primers were shown to have the highest amplification speed and detection performance in KDCC, of all modifications tested in this study, showing 10–100-fold lower detection limit but maintaining the same reaction time. Additionally, rapid herpes simplex virus detection system with azobenzene modified primers was developed. We believed that this breakthrough will contribute toward enabling greater utilization of POC-NATs for medical care, especially in developing countries and clinics. [ABSTRACT FROM AUTHOR]

A cost-effective microfluidic paper analysis device (μPAD) was developed with a special Z-folding design for controlling the fluidic flowing and substrate transportation. This presented μPAD can be easily fabricated through wax printing by using a solid ink printer which deposits wax onto the surface of a chromatographic paper, and then baked on a hotplate by penetrating the molten wax into the paper to create a hydrophobic barrier. After μPAD fabrication, liquid control and substrate transportation can be easily carried out by twice folding the μPAD following Z shape. The Z folding made two separated reagent holding zone connected while the detection reaction occurred with the connection. In this paper, a pathogens detection indicated by ATP quantification was took as a proof-in-principle application of using this presented μPAD, the limit of detection (LOD) was 1 μM for ATP detection and 2.6×10 7 CFU/mL for Salmonella live cell detection, which showed a great potential for Point-of-Care Testing (POCT) applications. [ABSTRACT FROM AUTHOR]

Abstract: In the proposed simple, disposable forced flow paper chromatographic device the main features of the separation like the analysis of time, separation power were improved. The chromatographic paper strips embedded into a polydimethylsiloxane (PDMS) block can be considered as an adsorption column, on which the liquid can be pumped. In a single device numerous separations can be performed in multiplex mode. On-capillary spectrophotometric detection is capable to detect the separated zones with good sensitivity. [Copyright &y& Elsevier]

Abstract: Large-scale open burning of joss paper is an important ritual practice for deity worshipping during Buddhist and Taoist festivals. Since Buddhism and Taoism are two of the most popular religions in Chinese societies and some Asian countries, the impact of joss paper burning on the air quality needs further investigation. This study explores the concentrations of polycyclic aromatic hydrocarbons (PAHs) in ambient air during one of the most important festivals, in which large-scale burning of joss paper occurs in temples and in people''s houses. The PAH concentrations were measured simultaneously at a temple site and a background site during both the festival and non-festive (ordinary) periods. Each ambient sample was extracted by the Soxhlet analytical method (for both particle-bound and gas-phase) and analyzed with gas chromatography. Experimental results indicate that the total PAH concentration during the festival period is approximately 4.2 times higher than that during the ordinary period (5384ngm−3 vs. 1275ngm−3). This study also employed statistical methods including diagnostic ratios and principal component analysis (PCA) to identify the possible PAH emission sources. Joss paper burning and vehicular emissions are identified as the principal sources of airborne PAHs during the large-scale open-burning event. The results of this work provide useful information for public awareness concerning PAH emission from the open burning of joss paper. [Copyright &y& Elsevier]

Paper chromatography was a big breakthrough in the early of 20th century but it is rarely used due to the long separation time and the diffusion on the sample spots. In this work, for the first time, a paper-based chemiluminescence (CL) analytical device combined with paper chromatography was developed for the determination of dichlorvos (DDV) in vegetables without complicated sample pretreatment. The paper chromatography separation procedure can be accomplished in 12min on a paper support (0.8×7.0cm2) by using 5µL sample spotted on it. After sample developing, the detection area (0.8×1.0cm2) was cut and inserted between two layers of water-impermeable single-sided adhesive tapes. The paper-based chip was made by attaching the middle layer of paper onto the bottom layer. Then it was covered by another tape layer, which was patterned by the cutting method to form a square hole (0.8×1.0cm2) in it. 10μL mixed solution of luminol and H2O2 was dropped on the detection area to produce CL. A linear relationship was obtained between the CL intensity and the concentrations of DDV in the range between 10.0ngmL−1 and 1.0μgmL−1and the detection limit was 3.6ngmL−1. Water-soluble metal ions and vitamins can be developed at different spatial locations relative to DDV, eliminating interference with DDV during detection. The paper-based chromatographic chip can be successfully used for the determination of DDV without complicated sample preparation in vegetables. This study should, therefore, be suitable for rapid and sensitive detection of trace levels of organophosphate pesticides in environmental and food samples. [ABSTRACT FROM AUTHOR]

Abstract: A solid-phase microextraction (SPME) method has been developed for the determination of pentachlorophenol (PCP) in paper and board samples. The analytical procedure involves direct extraction of PCP from paper and board samples and determination by gas chromatography with electron capture detection (GC–ECD). Two kinds of commercially available fibres; 100μm polydimethylsiloxane (PDMS), apolar, and 85μm polyacrylate (PA), quite polar, were evaluated to determine the extraction efficiency of pentachlorophenol. Parameters affecting the extraction process, such as temperature and time, were studied. Moreover, time of desorption and the effect of addition of salt were also investigated. The optimized procedure was applied to the analysis of pentachlorophenol (PCP) in five samples of virgin and recycled paper and board. The PCP content was determined by GC–ECD. To evaluate the effectiveness of the proposed method, it was compared with conventional extraction method with liquid–liquid extraction and derivatization. Detection limit of 0.015μg/g for PCP in paper was achieved with a RSD of 14%. [Copyright &y& Elsevier]

Noroviruses are the most common cause of nonbacterial gastroenteritis outbreaks. A novel method was tested that utilizes sodium dodecyl sulfate (SDS)/EDTA-pretreated chromatography paper strips to collect and transport norovirus-containing fresh stool samples. As confirmation, the strips were infected with different dilutions of human norovirus-containing faeces and stored at different temperatures (-80, -20, 4°C, room temperature and 37°C). Reverse transcription (RT)-PCR analysis was carried out after storage of the strips for 1, 7, 14, 60, and 120 days. The presence of amplifiable norovirus RNA on the strips was inversely correlated with the duration of storage and the storage temperature. Norovirus RNA remained detectable for a sufficient amount of time at room temperature or even in warmer climatic conditions to allow transportation of the samples from a field site to a reference laboratory using regular postal mail. To prove that viral infectivity was lost upon contact with the SDS/EDTA-treated strips, feline calicivirus F9 (107 TCID50/ml) was loaded onto the strips. After elution and dialysis, no cytopatic effect could be observed upon incubation on Crandell–Reese feline kidney cells. The SDS/EDTA-pretreated chromatography filter paper strips are an inexpensive, biosafe and adequate method to collect, transport and store norovirus samples. [Copyright &y& Elsevier]

In this work, a novel analytical approach based on the photocatalytic decomposition of N -nitrosamines combined with headspace thin-film microextraction of the generated nitrogen oxides such as NO has been developed for the determination of the acyclic N -nitrosamine fraction in drinking water samples. A hydrophilic cellulose substrate modified with fluorescent silver nanoclusters (Ag NCs) was used both as extractant and sensing platform. A quenching effect of Ag NCs fluorescence occurs as the concentration of N -nitrosamines increases. Front-face fluorescence spectroscopy with a solid sample holder was employed for directly measuring the fluorescence quenching onto the cellulose substrate. In order to achieve an optimal analytical response, different parameters involved in the photocatalytic reaction as well as those concerning the microextraction step were fully investigated. It is demonstrated that the photodegradation rate of cyclic N -nitrosamines at acidic pH is much lower than that of acyclic ones, which can be the basis for the determination of the later fraction in waters. Under optimal conditions, a detection limit for the acyclic N -nitrosamine fraction around 0.08 μg L−1 using N -nitrosodimethylamine (NDMA) as model compound for calibration was obtained. Several drinking waters were spiked with acyclic N -nitrosamines showing recoveries in the range of 98–102% with a relative standard deviation of 3–4% (N = 3). N -nitrosamines generated as by-products during disinfection processes applied to water cause multiple adverse effects on human health being classified as potential human carcinogens. This study highlights the suitability of a fluorescent paper-based sensor for the rapid analysis of the acyclic N -nitrosamine fraction (i.e. the most abundant fraction) as a total index in drinking water, being useful as screening tool before exhaustive chromatographic analysis, which saves costs, time and reduces waste generation. [Display omitted] • In situ photocatalytic decomposition of N -nitrosamines to NO x species is performed. • Combination of microextraction with fluorescent paper-based sensing for NO x detection. • Ag NCs immobilized onto cellulose behave both as sorption and sensing platforms. • Front-face fluorescence spectroscopy as readout technique in the paper-based sensor. • A simple and rapid method for acyclic N -nitrosamines detection is accomplished. [ABSTRACT FROM AUTHOR]

This study demonstrates chromatic analysis based on a simple red green blue (RGB) color model for sensitive and selective determination of mercury(II). The analysis was performed by monitoring the color change of a microfluidic Paper-based Analytical Device (µPAD). The device was fabricated by using alkyl ketene dimer (AKD)-inkjet printing and doped with unmodified silver nanoparticles (AgNPs) which were disintegrated when being exposed to mercury(II). The color intensity was detected by using an apparatus consisting of a digital camera and a homemade light box generating constant light intensity. A progressive increase in color intensity of the tested area on the µPAD (3.0 mm) was observed with increasing mercury(II) concentration. The developed system enabled quantification of mercury(II) at low concentration with the detection limit of 0.001 mg L −1 (3 SD blank/slope of the calibration curve) and small sample volume uptake (2 µL). The linearity range of the calibration curve in this technique was demonstrated from 0.05 to 7 mg L −1 (r 2 =0.998) with good precision (RSD less than 4.1%). Greater selectivity towards mercury(II) compared with potential interference ions was also observed. Furthermore, the percentage recoveries of spiked water samples were in an acceptable range which was in agreement with the values obtained from the conventional method utilizing cold vapor atomic absorption spectrometer (CVAAS). The proposed technique allows a rapid, simple, sensitive and selective analysis of trace mercury(II) in water samples. [ABSTRACT FROM AUTHOR]

Background: Fingertip prick whole blood collection on chromatography paper is amenable to high-throughput fatty acid (FA) profiling for large clinical and field studies. However, sample storage is problematic because highly unsaturated FAs (HUFAs) in erythrocytes rapidly degrade in samples stored at -20°C. Objective: The aim of the current study was to determine the mechanism of HUFA degradation and to develop prevention protocols. Methods: Free fatty acid (FFA) standards and whole blood reference material from a single participant were used to examine sample storage at -20°C for up to 90 d in triplicate. Iron chelation with deferoxamine (0-5000 µg), antioxidant protection with butylated hydroxytoluene (50 µg), cryopreservation with glycerol, and blood drying were examined using whole blood on chromatography strips. Biological replicate blood samples from additional participants (n = 6) with a range of ω-3 (n-3) HUFA concentrations were similarly assessed. Results: FFAs were relatively stable when stored on chromatography strips at -20°C. Glycerol treatment prevented HUFA degradation in whole blood reference material for 30 d (45 ± 0.4 to 46.8 ± 0.1, means ± SDs) compared to untreated saline controls (45.9 ± 1.0 to 6.8 ± 0.2). Pretreatment of paper for blood spots with deferoxamine and drying blood before storage slowed, but not entirely prevented, HUFA degradation over 30 d to 22% and 19% below baseline, respectively, compared to 86-92% in the controls. Protection against HUFA degradation with blood drying and glycerol treatment was confirmed in the biological replicate study and confirmed by prevention of cell lysis. Conclusions: HUFA degradation during storage at -20°C appears to be due to hemolysis and subsequent iron-initiated peroxidation. This degradation may be prevented by glycerol, iron chelation, and/or dried blood spotting. A more thorough understanding of methods to prevent degradation during storage is critical with increasing use of FA profiling in large clinical studies. [ABSTRACT FROM AUTHOR]

Abstract: The diffusive gradients in thin films (DGT) technique has shown enormous potential for labile metal monitoring in fresh water due to the preconcentration, time-integrated, matrix interference removal and speciation analytical features. In this work, the coupling of energy dispersive X-ray fluorescence (EDXRF) with paper-based DGT devices was evaluated for the direct determination of Mn, Co, Ni, Cu, Zn and Pb in fresh water. The DGT samplers were assembled with cellulose (Whatman 3 MM chromatography paper) as the diffusion layer and a cellulose phosphate ion exchange membrane (Whatman P 81 paper) as the binding agent. The diffusion coefficients of the analytes on 3 MM chromatography paper were calculated by deploying the DGT samplers in synthetic solutions containing 500μgL-1 of Mn, Co, Ni, Cu, Zn and Pb (4L at pH 5.5 and ionic strength at 0.05molL-1). After retrieval, the DGT units were disassembled and the P 81 papers were dried and analysed by EDXRF directly. The 3 MM chromatographic paper diffusion coefficients of the analytes ranged from 1.67 to 1.87×10-6 cm2 s-1. The metal retention and phosphate group homogeneities on the P 81 membrane was studied by a spot analysis with a diameter of 1mm. The proposed approach (DGT-EDXRF coupling) was applied to determine the analytes at five sampling sites (48h in situ deployment) on the Piracicaba river basin, and the results (labile fraction) were compared with 0.45μm dissolved fractions determined by synchrotron radiation-excited total reflection X-ray fluorescence (SR-TXRF). The limits of detection of DGT-EDXRF coupling for the analytes (from 7.5 to 26μgL-1) were similar to those obtained by the sensitive SR-TXRF technique (3.8 to 9.1μgL-1). [Copyright &y& Elsevier]

Abstract: A reversed-phase high performance liquid chromatographic method was developed and validated for the quantitative determination of amodiaquine (AQ) and its metabolite desethylamodiaquine (DAQ) in whole blood collected on filter paper. The structure analogue 4-(4-dimethylamino-1-methylbutylamino)-7-chloroquinoline was used as internal standard. Upon collection, blood was added to 10% phosphoric acid in a 1:1 ratio and then spotted onto filter paper. The samples were alkalinized (pH≈9.2) with potassium hydroxide at the time of assay and the compounds were extracted together with internal standard into di-isopropyl ether and then re-extracted into an aqueous phase with 0.1M phosphate buffer at pH 4. The chromatographic analysis was performed using an Agilent Technologies ChemStation LC System. The absorbance of the compounds was monitored at 333nm. Mean extraction recoveries of AQ and DAQ were 49 and 48%, respectively. Intra-day and inter-day coefficients of variation were <10.5%. The limit of quantification was 50nM for both compounds (sample size 100μl). Both AQ and DAQ that were previously reported to be unstable have been stored on filter paper for at least 19 weeks. The method was applied on samples from healthy volunteers. [Copyright &y& Elsevier]

Abstract: Pulp and paper mill wastewater was characterizated, before (influent) and after (effluent) biological wastewater treatment based on an activated sludge process, by microfiltration (8, 3, 0.45 and 0.22μm) and ultrafiltration (100, 50, 30 and 3kDa) of the wastewater samples into different size fractions. Various parameters were measured on each fraction: molecular weight distribution (MWD) using high performance size exclusion chromatography (HPSEC), total organic carbon (TOC), biochemical oxygen demand (BOD), chemical oxygen demand (COD), total phosphorus (Tot-P), phosphate phosphorus (PO4-P), electrical conductivity, pH, turbidity, charge quantity and zeta potential. The MWD, TOC and CODCr results indicated that the majority of the material present in both the influent and effluent was in the medium molecular weight (MW) range (i.e. MW<10kDa) with three main MW sub-fractions. There were no significant differences in the range of the MWD between the influent and effluent samples. The magnitude of the MWD in the effluent was about one half that in the influent, the greatest reduction being in the 6kDa fraction. The 3kDa fractions of both the influent and effluent showed a considerable increase in BOD7, probably due to the removal of compounds harmful to bacteria in 3kDa ultrafiltration. Influent turbidity decreased considerably in microfiltration (8–0.22μm). As the turbidity was removed by 0.22μm filtration, the anionic charge quantity started to decrease. Particles in the influent and effluent contained 19–29% and 14–20% of the total phosphorus, respectively. The major phosphorus fraction was in the form of soluble phosphate. [Copyright &y& Elsevier]

Abstract: A bioanalytical method for the determination of lumefantrine in 100μl blood applied onto sampling paper, by solid-phase extraction and liquid chromatography, has been developed and validated. Whatman 31 ET Chr sampling paper was pre-treated with 0.75M tartaric acid before sampling capillary blood to enable a high recovery of lumefantrine. Lumefantrine was extracted from the sampling paper, then further purified using solid-phase extraction and finally quantified with HPLC. The between-day variation was below 10% over the range 0.4–25μM. The lower limit of quantification was 0.25μM in 100μl capillary blood. No decrease in lumefantrine concentration in dried blood spot is seen after 4 months storage at 22°C. The method was also evaluated in field samples from patients in Tanzania after treatment with lumefantrine/artemether. Lumefantrine could be estimated accurately enough to assess bioavailability and treatment compliance on day 7 (i.e. 4 days after the last dose) after a standard regimen with the lumefantrine/artemether combination. [Copyright &y& Elsevier]

Natural killer (NK) cells are immune cells that defend against viral infections and cancer and are used in cancer immunotherapies. Subpopulations of NK cells include CD56dim and CD56bright which either produce cytokines or cytotoxically kill cells directly. The absolute number and proportion of these cells in peripheral blood are tied to proper immune function. Current methods of cytokine detection and proportion of NK cell subpopulations require fluorescent dyes and highly specialized equipment, e.g., flow cytometry, thus rapid cell quantification and subpopulation analysis are needed in the clinical setting. Here, a smartphone-based device and a two-component paper microfluidic chip were used towards identifying NK cell subpopulation and inflammatory markers. One unit measured flow velocity via smartphone-captured video, determining cytokine (IL-2) and total NK cell concentrations in undiluted buffy coat blood samples. The other, single flow lane unit performs spatial separation of CD56dim and CD56bright and cells over its length using differential binding of anti-CD56 nanoparticles. A smartphone microscope combined with cloud-based machine learning predictive modeling (utilizing a random forest classification algorithm) analyzed both flow data and NK cell subpopulation differentiation. Limits of detection for cytokine and cell concentrations were 98 IU/mL and 68 cells/mL, respectively, and cell subpopulation analysis showed 89% accuracy. • First smartphone-based paper microfluidic cell chromatography that can identify cell subpopulation. • Machine learning predictive modeling for NK cell subpopulation differentiation. • Integration of both cell chromatography and flow rate analysis on a single platform. • Potential application to many other cytokines and cell subpopulation analyses. [ABSTRACT FROM AUTHOR]

Abstract: A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography–mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25–125μgkg-1 for OP and 9.50–950μgkg-1 for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56μgkg-1 for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211μgkg-1. [Copyright &y& Elsevier]

Abstract: Environment-responsive membranes were prepared by coating filter paper with poly (N-vinylcaprolactam) hydrogel. These membranes could be made to switch between hydrophobic and hydrophilic states in a reversible manner by the addition or removal of lyotropic salts. The effects of polymer loading and salt concentration on hydraulic permeability and human immunoglobulin G (hIgG) binding property of these membranes were studied. A candidate membrane possessing high hydraulic permeability and hIgG binding property was selected for carrying out protein purification experiments. This membrane demonstrated selective antibody binding, and could be used for hIgG purification from simulated cell culture supernatant. [Copyright &y& Elsevier]

Abstract: Results presented in this paper demonstrate that time of flight secondary ion mass spectrometry (TOF-SIMS) can be used for the analysis of ballpoint pen inks producing mass spectra that were highly characteristic of the constituent dyes and inorganic substances used in their formulations. Analysis was performed directly off the substrate (typically document paper) containing the ink with no interference from the background matrix. The resultant spectra were highly characteristic of the ink formulation and could be used to confidently discriminate between different inks. No extraction or complicated sample preparation was necessary which ensures the integrity of the document under examination. This is not only important in forensic applications but also indicates the potential for the application of this technique to the analysis of inks on documents of historical or archaeological significance. TOF-SIMS was also shown to be capable of analysing ink containing a mixture of dyes, initially separated by thin-layer chromatography, directly on the chromatographic material. [Copyright &y& Elsevier]

Abstract: The determination of perfluorooctanoate (PFO) in articles of commerce has become increasingly important to understand if treated products are a possible source of PFO. An LC–MS/MS method for the determination of PFO in paper and textile using a dual labeled 13C-PFOA internal standard was successfully developed and validated. Residues of PFO were determined using an isocratic, reversed-phase high-performance liquid chromatography (HPLC) method with an ammonium acetate/methanol buffer. Ions monitored were 413 (parent) and 369 (daughter) for PFO and 415 (parent) and 370 (daughter) for dual labeled 13C-PFOA internal standard. As a precaution against ubiquitous PFO that occasionally occurs in mobile phase or instrument components, two Hypercarb™ cartridges (4mm) were placed before the HPLC injector. Any PFO that was captured by the cartridges was removed before each injection by flushing the system with 100% methanol prior to equilibration with the isocratic mobile phase. Overall recovery and standard deviation over a 3 day validation regimen for samples (n =54–55) fortified with PFOA at 5, 50, and 200ngg−1 were 114±4.9% for textile and 110±7.6% for paper. The results also established a limit of detection (LOD) of 1ngg−1 in textile and 2ngg−1 in paper based upon S/N of the 5.0ngg−1 fortification versus the untreated paper and textile. [Copyright &y& Elsevier]

Abstract: A comprehensive method for the determination of four stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWAs) in paper materials (napkin and paper tissue) and infant clothes was developed. FWAs were extracted from paper material and cloth samples using a hot-water extraction, and the aqueous extracts were then preconcentrated with the newly developed Oasis WAX (mixed-mode of weak anion exchange and reversed-phase sorbent) solid-phase extraction cartridge. The analytes were unequivocal determined by ion pair chromatography coupled with negative electrospray ionization-tandem mass spectrometry (HPLC-ESI–MS–MS), applying a di-n-hexyl-ammonium acetate (DHAA) as the ion-pairing reagent in mobile phase. Limits of quantitation (LOQ) were established between 0.2 and 0.9ng/g in 2g of samples. Recovery of five FWAs in spiked commercial samples was between 42 and 95% and RSD (n =3) ranging from 2 to 11%. The method was finally applied to commercial samples, showing that two stilbene-type disulfonates were predominant FWAs detected in napkin and infant cloth samples. [Copyright &y& Elsevier]

Hydrolytic degradation of cellulose was shown to take place during the activation procedure in distilled water during the dissolution procedure of cellulose samples from papers for size-exclusion chromatography analyses in the lithium chloride–N,N-dimethylacetamide (DMAc) solution system. The use of dilute aqueous sodium hydroxide solution in the activation procedure prevents hydrolytic degradation of cellulose during the dissolution procedure, especially in the case of samples of aged papers with low pH. The use of the freeze-drying technique provides samples of cellulose ready-made for dissolution in lithium chloride–N,N-dimethylacetamide solution. [Copyright &y& Elsevier]

Two extracellular alkalistable 1,4-β-d-glucan-4-glucanohydrolase (EC 3.2.1.4) fractions, namely Endo A and Endo B were separated from the culture filtrate of an alkalotolerant Fusarium strain by gel chromatography on Bio Gel P-100 column. The viscometric characterization of enzyme indicated that the Endo B was 1.9 times more random in action as compared to Endo A. Both the endoglucanases showed comparable patterns of their ability to release short fibers in the reaction mixture when filter paper was used as the substrate. The average size of released short fibers was determined by scanning electron microscopy ranged between 20 and 100 μm. Adsorption characteristics of the endoglucanases indicated that the enzyme complex acts prominently at the surface of substrate rather than at their cracked edges. The X-ray diffractograms showed that the crystallinity of the substrates does not vary significantly in the initial stages of the enzymatic action. The extracellular enzyme preparation was found to be suitable for deinking of mixed office waste papers. The enzyme treatment resulted in the increase in brightness with the reduction in ink counts of the recycled paper. Based on the distinct properties of endoglucanases a probable mechanism of enzymatic deinking process is presented schematically. [Copyright &y& Elsevier]

Abstract: The bacteria originated from the paper mill sludge were identified, isolated and cultured. Enterobacter (E) and Klebsiella (K) represented 70% of the culturable aerobic flora. Kinetics of EPS production in isolated culture and in arbitrary 1:1 mixture was investigated by high-pressure size exclusion chromatography (HPSEC). In isolated culture, Enterobacter produced regularly and gradually during 24h of culture, while Klebsiella produced the total amount of EPS already after 4h without any changes later. The chromatographic profiles of the EPS production of the 1:1 mixture after 4, 8 and 24h of culture could be fitted as a linear combination of the profiles of exopolymers produced by pure Enterobacter and Klebsiella strains. After 24h of culture, Enterobacter was predominant in term of population (82%) and produced about 77% EPS amount, in spite of competition phenomena observed during culture. [Copyright &y& Elsevier]

Abstract: Residual lignins were isolated from eucalypt kraft pulps by enzymatic hydrolysis of cellulose followed by purification using a combination of proteinase hydrolysis and solvent extraction. The residual lignins isolated from brown (unbleached) and totally chlorine free (TCF) bleached pulps were analyzed by Fourier-transform infrared (FT-IR) spectroscopy and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and compared with eucalypt milled-wood lignin and kraft lignin. The lignin in eucalypt wood and pulps showed a strong predominance of syringyl (S) over guaiacyl (G) units. The strongest lignin modification was observed in the kraft lignin recovered from the alkaline pulping liquor. The chemical composition of the residual lignin from pulp was closer to milled-wood lignin than to the kraft lignin, indicating that most of the lignin modified during pulping was released to the cooking liquor. During TCF bleaching of pulp, which included oxygen delignification and peroxide stages, modifications of lignin were produced resulting in increased amount of non-conjugated carbonyl groups. We concluded that residual lignin in eucalypt kraft pulp reflects native lignin moieties entrapped into the cellulosic network thus partially avoiding their attack by chemical reagents, although different modifications are produced during the bleaching stages. [Copyright &y& Elsevier]

Abstract: In the present paper, we report an improved ion-pair solid-phase extraction (IP-SPE) method for the analysis of alkylphosphonic acids, namely, methyl, ethyl and propylphosphonic acids, present in the aqueous sample. The aqueous sample was mixed with an ion-pair reagent, phenyltrimethylammonium hydroxide (PTMAH) and passed through activated charcoal SPE cartridge. The retained chemicals in the cartridge were extracted with methanol and analysed by gas chromatography–mass spectrometry (GC–MS) under the electron impact ionization (EI) mode. The analytes were converted to their methyl esters by pyrolytic methylation in the hot GC injection port. The recoveries of alkylphosphonic acids were above 95% and the minimum detection limits were as low as 10ng/mL. The recovery of the test chemicals was tested with solvents, dichloromethane, n-hexane, ethyl acetate, acetone, acetonitrile and methanol. The chemicals could be efficiently extracted by the hydrophilic solvents. The method did not work at the highly acidic pH (when acidified with dilute HCl) but worked well from pH 4.0 to 14.0. The present method was also tested with other tetra-(methyl, ethyl, propyl and n-butyl)ammonium hydroxides. The test chemicals were not converted to their methyl and ethyl esters with tetramethyl and tetraethylammonium hydroxides, whereas they were converted to their corresponding propyl and n-butyl esters with tetrapropyl and tetra(n-butyl)ammonium hydroxides. The method was also applied to two highly cross-linked polymeric sorbents DSC-6S and Oasis HLB. The recovery of the chemicals on these sorbents was observed to be poor. Methylation using phenyltrimethylammonium hydroxide is non-hazardous and advantageous over methylation using diazomethane. The method was applied to the analysis of aqueous samples given in one of the official proficiency tests conducted by the Organization for the Prohibition of Chemical Weapons and all the spiked chemicals were identified as methyl esters. [Copyright &y& Elsevier]

Abstract: The chemical warfare agents (CWA) degrade rapidly in aqueous samples and convert to acidic degradation products. Extraction and identification of the degradation products from complex matrices using simple sample preparation and sensitive detection and identification is the most important step in the off-site analysis of samples. In this present study, we report a simple sample preparation step based on ion-pair (IP) solid-phase extraction (SPE) for the extraction of acidic degradation products of CWA namely methyl, ethyl, propyl phosphonic acids, thiodiglycolic acid and benzilic acid. The analysis was performed on GC–MS in electron impact ionization mode. Three IP reagents triethylamine (TEA), tetrabutylammonium bromide (TBAB) and cetyltrimethyl ammonium bromide (CTAB) were used. The recoveries were estimated using the internal and external standard methods. The recovery of the compounds was almost negligible when TEA was used as IP reagent. The recoveries obtained when TBAB and CTAB were used as IP reagents were high and reproducible. The recovery of test chemicals is above 90%, except for methyl phosphonic acid and ethylphosphonic acid (20.6±3.2% and 35.8±2.5%, respectively). The minimum detection limits of the method were calculated for all chemicals in both full scan and selected ion monitoring modes. The test chemicals could be detected in microgram per litre quantities by the IP–SPE method. [Copyright &y& Elsevier]

Abstract: Often the evaluation of the best chemical agent to be used in ultrafiltration (UF) and microfiltration (MF) membrane processes is a trial and error process usually derived from pilot plant experiments in half technical scale. This is expensive and time-consuming as the membranes have to be fouled again after the cleaning step. To overcome this problem, a single membrane capillary test unit for testing out-in capillaries was used. The major benefit is the possibility of investigating the performance of different cleaning agents at several capillaries, which were fouled comparably as they were taken out of the same module. Within this study 16 capillaries were cleaned with different cleaning agents of the categories oxidants, bases and acids, alone or in combination with each other at two different temperatures. After each cleaning step the cleaning solution was gathered and analysed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) on inorganic and Liquid Chromatography-Organic Carbon Detection (LC-OCD) on organic eluted foulants to evaluate how the foulants are affected by the different cleaning agents. Additionally, the permeability before and after each elution experiment was measured in order to determine the cleaning efficiency. Based on the results proposals for the use of specific cleaning agents for specific fouling substances are derived. [Copyright &y& Elsevier]