based on reversed SPE columns fille

based on reversed SPE columns filled with Hydrophilic-Lipophilic
Balance (HLB), divinylbenzene-N-vinylpyrrolidone copolymer or
C18 stationary phases, while the use of molecularly imprinted
polymers (MIP) is also reported for the determination of BPA in biological matrices [8]. Additionally, other extraction techniques are
available and may be use for BPA extraction purpose, such as solidphase microextraction (SPME) [9], matrix solid-phase dispersion
(MSPD) or stir bar sorptive extraction (SBSE) [10].
Liquid chromatography–mass spectrometry (LC–MS) is often
preferred to gas chromatography–mass spectrometry (GC–MS) as
it does not need any derivatization step prior chromatographic
separation. However, the major drawback of LC-MS methodology
remains charge competition observed in electrospray ionization
leading to questionable results especially when complex biological
matrices – such as foodstuffs – are concerned [11–13].
The use of GC–MS has been chosen by several authors for
the analysis of BPA in certain categories of food items [14–18].
Nevertheless, a drastic standard operating procedure has to be
applied to allow an efficient derivatization of the targeted molecule.
Indeed, the presence of residual lipids competes for the reagent
and impact significantly the derivatization efficiency and thus the
global analytical performances of the method [19–21]. Silylation
using MSTFA, BSTFA or MTBSTFA have been very often reported for
BPA analysis [5,16,22–35] while BSTFA is the most frequently used.
Such strategy has successfully been applied for the determination of
BPA in several complex matrices, such as meat, fish, fruits, vegetables and numerous solid food items [16,25,27,29,36–38]. Moreover,
while tandem mass spectrometry (MS/MS) [17,18] or high resolution mass spectrometry (HRMS) may be available as detection
technique, GC–MS is usually implemented in combination with
either no use of any internal standard or the use of deuterated BPA.
Therefore, analytical performances as published in the literature
are difficult to compare in terms of performances. Reported detection and quantification limits are significantly different insofar as
reported detection limits ranged from 0.4 ng L
−1
in food stimulant
[39] without any internal standard used to 1 g kg
−1
in beverages
[37] using BPA-d14 as internal standard. Regarding the complex
matrices such as fish [36], a LOD of 0.41 g kg
−1
was reported
using BPA-d16as internal standard. Nevertheless, few of the published analytical methods are fully validated in particular regarding
trueness and accuracy.
The ubiquitous character of BPA is an additional challenge of
BPA analysis [40,41]. From the sampling of the food items until the
spectrometric signal production, BPA may enter unintentionally in
the analytical chain. Sample collection material, analytical glassware, SPE cartridges, solvents, ultrapure water, various parts of the
chromatograph are potentially BPA sources; they have to be tested
before use and regularly checked batch-to-batch [3]. It is highly
recommended to establish “blank” control chart to accept/reject
analytical batches as well as to determine a concentration level
below which it is not reasonable to report values for the samples.
Method validations follow different standards such as
2002/657/EC decision [42] and/or LAB GTA 26 [40] and
SANCO/10684/2009 guideline [43,44].
The analytical method presented in this paper has been developed in the frame of the 2nd French Total Diet Study (TDS). It
covers a large panel of solid and liquid foodstuffs and both detection and quantification limits performances were better than 0.03
and 0.09 g kg
−1
, respectively. Gas chromatography coupled to a
tandem mass spectrometry (triple quadrupole device) has been
preferred. Electron ionization and Selected Reaction Monitoring
were found optimal to assure the robust quantification of BPA in
foodstuffs. Quantification relied on the isotopic dilution principle
using
13
C12-BPA as internal standard. The standard operating procedure is based onto a first liquid–liquid or liquid–solid extraction,
depending on the matrix of interest and two consecutive solid
phase extractions (non-polar stationary phase and MIP) followed
by a derivatization step.
A particular attention was paid to environmental contamination by using a control chart with specified alert limits. Different
possible analytical pitfalls have been pointed out during the study
and propositions to manage them have been proposed. A validation
protocol was eventually performed; performances are discussed in
the light of exposure data generation.
2. Materials and methods
2.1. Standards and reagents
Bisphenol A [2,2-bis(4-hydroxyphenyl)propane, BPA] and
13
C12-BPA were obtained from Cambridge Isotope Laboratories
(Andover, MA, USA). Acetonitrile and methanol (HPLC gradientgrade quality), cyclohexane and formic acid were purchased from
Carlo-Erba Reagents (Rodano, Italy). Ultrapure water was purified using a Milli-Q-osmosis system from Millipore (Milford, MA,
USA). Both solid phase extraction columns, i.e. HR-X and Affinimip
BPA were obtained, respectively, from Macherey-Nagel (Hoerdt,
France) and Polyintell (Val de Reuil, France). The derivatization
reagent (N-methyl-N(trimethylsilyl)-trifluoroacetamide—MSTFA)
was purchased from Sigma-Aldrich (Saint Quentin Fallavier,
France).
Stock standard solutions of both BPA and
13
C12-BPA were prepared in acetonitrile at a concentration of 5 ng L
−1
. Working
solutions were obtained by an appropriate dilution in acetonitrile.
All standard solutions were stored at 4
◦
C, in the dark.
2.2. Scope of the analytical method
Samples analyzed in the French Total Diet Study (TDS2) were
included in the scope of the developed method. Therefore, a
list of more than 1200 food items or individual foods was concerned and was divided into around forty food groups including
bread and dried bread products, breakfast cereals, pasta, rice
and wheat products, croissant-like pastries, sweet and savoury
biscuits and bars, pastries and cakes, milk, ultra-fresh dairy products, cheese, eggs and egg products, butter, oils, margarine, meat,
poultry and game, offal, delicatessen meats, fish, crustaceans and
molluscs, vegetables (excluding potatoes), potatoes and potato
products, pulses, fruit, dried fruits, nuts and seeds, ice creams,
sorbets and frozen desserts, chocolate, sugars and sugar derivatives, water, non-alcoholic beverages, alcoholic beverages, coffee,
other hot beverages, pizzas, quiches and savoury pastries, sandwiches and snacks, soups and broths, mixed dishes, dairy-based
desserts, compotes and cooked fruit, seasonings and sauces, specific
foods.
2.3. Sample pretreatment
The analytical strategy was developed for the determination
of BPA in a wide number of different categories of foodstuffs as
expected in a total diet study. The matrices covered liquid food
items such as water, milk, oil, wine, soft drink, coffee, tea, cream, as
well as solid state matrices prepared as consumed such as vegetables, fruits, fish, crustacean, meat, ready-cooked dishes, biscuits,
chocolate, cheese, desserts. The equivalent of 5 g of sample were
homogenized after a milling step, and accurately weighted in a
polypropylene tube. Then, 50 L of an internal standard solution
(
13
C12-BPA, 0.5 ng L
−1
) were directly added to the samples and
mixed

Hasil (Bahasa Indonesia) 1:

Berdasarkan terbalik SPE kolom diisi dengan Hydrophilic-lipofilikKeseimbangan (HLB), kopolimer divinylbenzene-N-vinylpyrrolidone atauFase stasioner C18, sementara penggunaan molekuler tercetakpolimer (MIP) juga dilaporkan untuk penentuan BPA di biologis matriks [8]. Selain itu, adalah teknik ekstraksi lainnyatersedia dan dapat digunakan untuk tujuan ekstraksi BPA, seperti solidphase microextraction (SPME) [9], matriks solid-fase dispersi(MSPD) atau aduk bar ekstraksi sorptive (SBSE) [10].Spektrometri massa-kromatografi cair (LC-MS) adalah seringpilihan ke spektrometri massa-kromatografi gas (GC-MS) sebagaitidak perlu derivatisasi langkah sebelumnya kromatografipemisahan. Namun, kelemahan utama dari metodologi LC-MStetap menagih kompetisi yang diamati dalam ionisasi electrospraymengarah ke hasil dipertanyakan terutama ketika kompleks biologismatriks-seperti bahan makanan – yang bersangkutan [11-13].Penggunaan GC-MS telah dipilih oleh beberapa penulis untukAnalisis BPA dalam kategori tertentu barang makanan [14-18].Namun demikian, prosedur operasi standar drastis harusditerapkan untuk memungkinkan derivatisasi efisien molekul ditargetkan.Memang, kehadiran sisa lipid bersaing untuk reagentdan dampak signifikan efisiensi derivatisasi dan dengan demikianGlobal analitis pertunjukan metode [19 – 21]. Silylationmenggunakan MSTFA, BSTFA atau MTBSTFA telah sangat sering dilaporkan untukBPA analisis [5,16,22-35] sementara BSTFA adalah yang paling sering digunakan.Strategi tersebut berhasil diterapkan untuk penentuanBPA di beberapa matriks kompleks, seperti daging, ikan, buah-buahan, sayuran dan berbagai jenis makanan padat [16,25,27,29,36-38]. Selain itu,Sementara tandem spektrometri massa (MS/MS) [17,18] atau resolusi tinggi spektrometri massa (HRMS) mungkin akan tersedia sebagai deteksiteknik, GC-MS biasanya dilaksanakan dalam kombinasi denganbaik tidak menggunakan standar apapun internal atau penggunaan deuterated BPA.Oleh karena itu, analisis pertunjukan sebagai diterbitkan dalam literatursulit untuk membandingkan dalam pertunjukan. Melaporkan Deteksi dan kuantifikasi batas secara signifikan berbeda sejauhmelaporkan deteksi batas berkisar dari 0,4 ng L–1dalam makanan stimulan[39] tanpa standar apapun internal digunakan untuk 1 g kg–1dalam minuman[37] menggunakan BPA-d14 sebagai standar internal. Mengenai kompleksmatriks seperti ikan [36], LOD g 0,41 kg–1dilaporkanmenggunakan standar internal BPA-d16as. Namun demikian, beberapa metode analytical diterbitkan sepenuhnya divalidasi secara khusus mengenaitrueness dan akurasi.Karakter di mana-mana BPA adalah tantangan tambahanBPA analisis [40,41]. Dari sampling item makanan sampaiproduksi spectrometric sinyal, BPA bisa masuk tidak sengajarantai analitis. Contoh koleksi bahan, gelas analitis, SPE kartrid, pelarut, air ultrapure (murni), berbagai bagianChromatograph yang berpotensi BPA sumber; mereka harus diujisebelum menggunakan dan secara teratur memeriksa batch-batch ke-[3]. Sangat tinggidirekomendasikan untuk membentuk diagram kontrol "kosong" untuk menerima Tolakbatch analitis serta untuk menentukan tingkat konsentrasidi bawah ini yang sangat tidak masuk akal untuk laporan nilai untuk sampel.Validasi metode mengikuti standar yang berbeda seperti2002/657/EC keputusan [42] dan/atau LAB GTA 26 [40] danSANCO/10684/2009 pedoman [43,44].Metode analisis yang disajikan dalam tulisan ini telah dikembangkan dalam bingkai dari 2 Perancis Total Diet studi (TDS). Itumeliputi panel besar bahan makanan padat dan cair dan deteksi dan kuantifikasi batas kinerja yang lebih baik daripada 0.03dan 0,09 g kg–1, masing-masing. Kromatografi gas digabungkan ketandem spektrometri massa (triple quadrupole device) telahlebih disukai. Elektron ionisasi dan reaksi dipilih pemantauanditemukan optimal untuk memastikan kuantifikasi kuat BPA dibahan makanan. Kuantifikasi mengandalkan prinsip pengenceran isotopicmenggunakan13C12-BPA sebagai standar internal. Prosedur operasi standar didasarkan ke ekstraksi pertama cair-cair atau cair-padat,tergantung pada matriks minat dan dua berturut-turut padattahap ekstraksi (non-polar fase stasioner dan MIP) diikutioleh derivatisasi langkah.Perhatian dibayar untuk terjadinya pencemaran lingkungan dengan menggunakan diagram kontrol dengan batas waspada. Berbedaperangkap analitis yang mungkin telah menunjukkan selama studidan dalil mengelola mereka telah diajukan. Validasiprotokol akhirnya dilaksanakan; pertunjukan dibahas dalamcahaya paparan data generasi.2. bahan dan metode2.1. standar dan reagenBisphenol A [2,2-bis(4-hydroxyphenyl) propana, BPA] dan13C12-BPA Diperoleh dari Cambridge isotop laboratorium(Andover, MA, USA). Asetonitril dan metanol (HPLC gradientgrade kualitas), cyclohexane dan Asam formiat itu dibeli dariCarlo-Erba reagen (Rodano, Italia). Air ultrapure (murni) adalah dimurnikan menggunakan sistem Mili-Q-osmosis dari Millipore (Milford, MA,USA). Kolom ekstraksi padat tahap kedua, yaitu HR-X dan AffinimipBPA diperoleh, masing-masing, dari Macherey-Nagel (Hoerdt,Perancis) dan Polyintell (Val de Reuil, Perancis). Derivatisasireagen (N-methyl-N(trimethylsilyl)-trifluoroacetamide—MSTFA)dibeli dari Sigma Aldrich (Saint Quentin Fallavier,Prancis).Saham standar solusi BPA kedua dan13C12-BPA yang disiapkan di asetonitril pada konsentrasi 5 ng L–1. Bekerjasolusi yang diperoleh oleh diencerkan dalam asetonitril.Semua standar solusi disimpan di 4◦C, dalam gelap.2.2. lingkup metode analisisContoh yang dianalisis dalam Perancis Total Diet studi (TDS2) adalahtermasuk dalam lingkup metode yang dikembangkan. Oleh karena itu,Daftar lebih dari 1200 item makanan atau makanan individu prihatin dan dibagi menjadi kelompok-kelompok makanan sekitar empat puluh termasukroti dan roti kering produk, Sarapan sereal, pasta, nasidan produk gandum, kue-kue seperti croissant, manis dan gurihproduk susu ultra segar biskuit dan Bar, kue-kue dan kue, susu, keju, telur, dan telur, mentega, minyak, margarin, produk daging,unggas dan permainan, jeroan, toko makanan daging, ikan, krustasea danmoluska, sayuran (tidak termasuk kentang), kentang dan kentangproduk, kacang-kacangan, buah, buah-buahan kering, kacang-kacangan dan biji-bijian, es krim,sorbet, dan hidangan penutup, coklat, gula dan gula derivatif, air, minuman non-alkohol, minuman beralkohol, kopi,minuman panas lain, pizza, Pie dan kue-kue gurih, sandwich dan makanan ringan, sup dan kaldu, campuran hidangan, berbasis susumakanan penutup, compotes dan buah yang matang, bumbu dan saus, khususmakanan.2.3. sampel pretreatmentAnalisis strategi dikembangkan untuk penentuanBPA di sejumlah kategori yang berbeda bahan makanan sebagaidiharapkan dalam studi total diet. Matriks ditutupi makanan cairbarang-barang seperti air, susu, minyak, anggur, minuman ringan, kopi, teh, krim, sebagaiserta keadaan padat matriks disiapkan sebagai dikonsumsi sayuran, buah-buahan, ikan, crustacea, daging, hidangan dimasak siap, biskuit,cokelat, keju, makanan penutup. Itu setara dengan 5 gram sampelhomogen setelah langkah penggilingan, dan akurat berbobot dalampolipropilena tabung. Kemudian, 50 L larutan standar internal(13C12-BPA, 0,5 ng L–1) langsung ditambahkan ke sampel dancampuran