Simultaneous determination of twelve natural estrogens in dairy milk using liquid-liquid extraction and solid-phase extraction coupled with gas chromatography-mass spectrometry.

There have been many analytical methods for natural estrogens in commercial dairy milk samples, but in most of which, only four major estrogens (estrone (E1), 17ß-estradiol (E2), estriol (E3), and 17α-estradiol (αE2)) were included. This work developed an effective GC-MS analytical method for simultaneous analysis of twelve natural estrogens in commercial dairy milk sample, in which eight far-less well-known natural estrogens (2-hydroxyestone (2OHE1), 4-hydroxyestrone (4OHE1), 2-hydroxyestradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 16-epiestriol (16epiE3), 16α-hydroxyestrone (16αOHE1), 16-ketoestradiol (16ketoE2) and 17epiestriol (17epiE3)) were included besides the four major natural estrogens. With liquid-liquid extraction and solid phase extraction, twelve natural estrogens in commercial dairy milk could be effectively extracted. The established method showed good linearity (R2 > 0.9991), low limits of detections (LODs, 0.02-0.11 ng/g), as well as excellent recoveries (64-117%) with satisfactory low relative standard deviations (RSDs, 0.8-14.7%). This established method was applied to seven commercial dairy milk samples, and all the twelve natural estrogens were frequently detected except for 4OHE2 without detection in any sample. Our results showed that the concentration contribution ratios of the eight far-less well-known natural estrogens in commercial dairy milk samples contributed to 32-83%, while the corresponding contribution ratios based on estrogen equivalence (EEQ) were 21-62%. This work highlighted the high abundance of the eight far-less well-known natural estrogens in commercial dairy milk based on both concentration and EEQ, which has been neglected for a long time.

Twelve natural estrogens and ten bisphenol analogues in eight drinking water treatment plants: Analytical method, their occurrence and risk evaluation.

Bisphenol analogues (BPs) and natural estrogens (NEs) as two important groups of endocrine-disrupting compounds (EDCs) in drinking water treatment plants (DWTPs) have been hardly investigated except bisphenol A (BPA) and three major NEs including estrone (E1), 17ß-estradiol (E2) and estriol (E3). In this study, a GC-MS analytical method was firstly established and validated for trace simultaneous determination of ten BPs and twelve NEs in drinking water, which included BPA, bisphenol B (BPB), bisphenol C (BPC), bisphenol E (BPE), bsiphenol F (BPF), bsiphenol P (BPP), bisphenol S (BPS), bisphenol Z (BPZ), bisphenol AF (BPAF), bisphenol AP (BPAP), E1, E2, E3, 17α-estradiol (17α-E2), 2-hydroestrone (2OHE1), 16hydroxyestrone (16α-OHE1), 4-hydroestrone (4OHE1), 2-hydroxyesstradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 17-epiestriol (17epiE3), 16-epiestriol (16epiE3) and 16keto-estraiol (16ketoE2). This investigation showed that eighteen out of twenty-two targeted compounds were detected in drinking source waters of eight DWTPs with concentrations ranging from not detected to 142.8 ng/L. Although the conventional treatment process of DWTP could efficiently remove both BPs and NEs with respective removal efficiencies of 74.1%-90.9% and 74.5%-100%, BPA, BPS, BPE, BPZ, E1, 2OHE1, and 2OHE2 were found in the finished drinking waters. Chlorination could remove part of BPs and NEs, but the efficiency varied greatly with DWTP and the reason was unknown. In the finished drinking waters of eight DWTPs, the highest chemically calculated estrogen equivalence (EEQ) derived from BPs and NEs was up to 6.11 ngE2/L, which was over 22 times that could do harm to zebrafish, indicating a potential risk to human health. Given the fact that many chlorination products of BPs and NEs likely have higher estrogenic activities, the estrogenic effect of BPs and NEs in finished drinking water should be accurately examined urgently with the inclusion of BPs, NEs as well as their main chlorinated by-products. This study shed new light on the occurrence, removal, and potential estrogenic effects of BPs and NEs in DWTPs.

[Distribution, Sources, and Health Risk Assessment of PAHs in Water Supply Source Regions of Guangzhou].

Trace polycyclic aromatic hydrocarbons (PAHs) in drinking water sources have significant harmful effects on human health. Water and sediment samples from water source regions of three water treatment plants in Guangzhou were collected and the distributions of 16 kinds of PAHs were analyzed. The human risk of PAHs in the water samples was also evaluated using the Risk Assessment Guidance for Superfund (RAGS) of the United States Environmental Protection Agency (USEPA). The results showed that PAHs in the samples from the three water source regions did not exceed the corresponding standard limit for water quality, and the content of ΣPAHs in suspended solids and sediments was below the medium level. The non-carcinogenic risks (HQ and HI) of PAHs in the water samples were less than 1, and the non-carcinogenic risk was negligible. In addition, Riskingest, Riskdermal, and RiskT for the waters were all in range of 5.53×10-7 to 5.34×10-6, indicating that a carcinogen risk was possible but acceptable. The results of the isomer ratio method indicated that the PAHs in the water sources of the three water plants had a mixed input of pollution, including petroleum discharge, petroleum combustion, and incomplete combustion of wood, coal, and biomass. The total organic carbon (TOC) content of the water and sediment samples was positively correlated with the accumulation and enrichment of low-ring PAHs, and there was a significant positive correlation between PAHs and similar molecules in the sediments. The ΣPAHs in the water and sediment samples were also strongly correlated.

[Distribution Characteristics and Ecological Risk Assessment of Organochlorine Pesticides in Surface Sediments of Zhelin Bay in Guangdong Province, China].

The distribution characteristics and pollution degrees of 20 organochlorine pesticides (OCPs) were investigated in surface sediments from Zhelin Bay south of China and the ecological risk of OCPs and integrated ecological risk at the samples stations in sediments were evaluated by risk quotient (RQ) and sediment quality guideline of NOAA. The possible sources of HCHs and DDTs in sediments were preliminarily studied, and the correlation between OCPs and sediment characteristic parameters was discussed. The concentrations of DDTs in surface sediments were found to be higher than those of other OCPs, especially p,p'-DDD, and the concentrations of DDTs were higher than the limited values of Chinese Marine sediment quality criteria. The total concentration of 20 OCPs in surface sediments ranged from 14.14 to 306.88 ng·g-1, with a mean concentration of 78.37 ng·g-1, and the highest total concentration was at site 8(S8). There were inevitable adverse biological effects and high ecological risk of p,p'-DDD and p,p'-DDT, high integrated ecological risk at S8 and S10. The possible sources of HCHs in surface sediments of Zhelin Bay were mainly from the application of Lindane pesticides. At S1,S2,S10,S11 there was input of DDT into mariculture area of Zhelin Bay, and at the other sites the sources of DDT were from the early residue in sediments or the long-term weathering sediments of using pesticides. There was a very significant positive correlation between HCHs, endosulfan, chlordane and dieldrin in sediments, while there was a negative relation between the above OCPs and TOC, which indicated that the presence of TOC could promote their biodegradation. There was a significant positive correlation between p, p'-DDD and Ca, which revealed that DDT used in the early period was deposited with biological carbonate. Increasing size of sediment particles discouraged the accumulation and enrichment of OCPs in sediments.

A microporous metal-organic framework containing an exceptional four-connecting 4(2)6(4) topology and a combined effect for highly selective adsorption of CO2 over N2.

Reported here is a new microporous metal-organic framework, namely [Zn(2)(L)(btc)(Hbtc)] [NH(2)(CH(3))(2)]·(DMF)(2)(H(2)O)(4) (1), which is synthesized solvo(hydro)thermally by the self-assembly of Zn(NO(3))(2), N(4),N(4)-di(pyridin-3-yl)-[1,1'-biphenyl]-4,4'-dicarboxamide (L) and 1,3,5-benzenetricarboxylate acid (H(3)btc). Its topology can be described as a four-connecting 4(2)6(4) matrix containing both tetrahedral metal and ligand nodes. Interestingly, such a matrix has the same topology symbol as that observed in the well known sodalite (SOD) net, but the td10 of 434 is different from the td10 of 791 for the SOD net, indicative of an exceptional four-connecting 4(2)6(4) net. Another outstanding point is the highly selective adsorption of CO(2) over N(2), possibly contributed by a combined effect from the charged skeleton, the existence of functional groups of -CONH- and -COOH in 1.

Solvent-induced supramolecular isomers, structural diversity, and unprecedented in situ formation of both inorganic and organic ions in inorganic-organic mercury(II) complexes.

Reported here is, for the first time, an important study of solvent effect on structural diversity in inorganic-organic mercury(II) complexes. As a result, the first supramolecular isomer in mercury(II) complexes is obtained. Importantly, a previously unobserved in situ generation of both inorganic (Cl(-)) and organic ([CH(3)-L1-CH(3)](2+)) ions was also observed.

A self-catenated network containing unprecedented 0D + 2D → 2D polycatenation array.

Herein, we report a new acylamide ligand and its application in the construction of a metal-organic framework. The resultant acylamide metal-organic framework, namely [Zn(2)(L)(OH)(btc)](n) (1, L = N(1),N(4)-bis(pyridin-3-ylmethyl) naphthalene-1,4-dicarboxamide, H(3)btc = benzene-1,3,5-tricarboxylic acid), was obtained by hydrothermal synthesis. The outstanding structural feature of it is the 0D + 2D → 2D polycatenation array containing a self-catenated feature which has never previously been observed. To the best of our knowledge, the coexistence of self-catenation and polycatenation phenomena is highly exceptional.

Functionalizing the pore wall of chiral porous metal-organic frameworks by distinct -H, -OH, -NH2, -NO2, -COOH shutters showing selective adsorption of CO2, tunable photoluminescence, and direct white-light emission.

This work presents a prototype of chiral porous metal-organic framework with the porous wall decorated by different functional groups. The special structure in conjunction with the gas adsorption results reveals some relationship between CO2 adsorption and functional points. Moreover, outstanding tunable photoluminescence and direct white-light emission is observed.

A series of 1D Dy(III) compound showing slow magnetic relaxation: synthesis, structure, and magnetic studies.

In this work, we present the synthesis, structure, and magnetic studies of three 1D homo-spin Dy(III) compounds in detail. For 1, one crystallography-independent Dy(III) site is contained and the coordination surrounding is a distorted square-antiprism geometry. Within 2, four crystallography-independent Dy(III) sites with largely distorted square-antiprism geometry are observed. As for 3, two crystallography-independent Dy(III) sites showing bicapped triangular-prism geometry are involved. The magnetic studies suggest weak ferromagnetic interactions for 1 and weak antiferromagnetic interactions for 2 and 3. Their dynamic magnetic properties are investigated by means of alternating current (ac) susceptibility measurement, revealing their slow magnetic relaxation. Moreover, a field-dependent ac signal is observed in 1, when by applying a static dc = 1000 Oe field, strong frequency-dependent ac signals and the peak of out-of-phase (χ'') can be clearly found. Ultimately, by fitting the Arrhenius law the energy barrier and relaxation time are estimated.

The application of single-crystal-to-single-crystal transformation towards adjustable SMM properties.

Reversible single-crystal-to-single-crystal transformation (SCSC) was for the first time observed between 4f-based molecular magnets.

Chiral 1D Dy(III) compound showing slow magnetic relaxation.

Herein, we present one chiral Dy(III) compound, namely Dy(L)(3)(1, HL = 2-methylbenzoic acid), synthesized from the achiral HL ligand. Within 1, along a direction the seven-coordinated Dy(III) ion are bridged by double L carboxylate and single L oxygen to give rise to the 1D helical chain. The magnetic studies suggest small intra-chain ferromagnetic interactions. Alternating current (AC) magnetic measurements show a frequency dependence of magnetic susceptibilities in both in-phase, χ', and out-of-phase, χ''. However, no obvious peak can be found even under 1000 Oe static field, suggesting the prevalence of quantum tunnelling effect at low temperature.

Homochiral 1D zinc-quitenine coordination polymer with a high dielectric constant.

Heat treatment of a solution of MeOH and water containing the quitenine ligand HQA [HQA = 6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid] and ZnCl2 at 70 degrees C to give the one-dimensional (1D) chain coordination polymer {(HQA)(ZnCl2)(2.5H2O)}n (1). The local coordination geometry around the zinc center in 1 displays a slightly distorted tetrahedron, with the HQA ligand adopting a zwitterionic moiety similar to that found in natural amino acids. Measurements on a powdered sample of 1 reveal a strong second-harmonic-generation response of ca. 20 times larger than that for KDP (KH2PO4). Notably, measurements on the dielectric properties of 1 showed that the 1D chain coordination polymer exhibited a dipolar chain relaxation process and a high dielectric constant (epsilon0= 37.3).

Ferroelectric metal-organic framework with a high dielectric constant.

Hydrothermal reaction of (l)-N-(4'-cyanobenzy)-(S)-proline with CdCl2 as a Lewis acid catalyst and NaN3 gives colorless block compound 1, in which 1 displays a complicated 3D framework. Ferroelectric and dielectric property measurements reveal that 1 exhibits physical properties comparable to that of a typical ferroelectric compound with a dipole relaxation process and a dielectric constant of ca. 38.6 that makes it, by definition, a high dielectric material.

A second-order nonlinear optical material prepared through in situ hydrothermal ligand synthesis.

The in situ hydrothermal reactions of ZnCl(2) with benzonitrile, 2-amino-5-cyanopyridine, and trans-2,3-dihydro-2-(4' '-cyanophenyl)-benzo[e]indole in the presence of NaN(3) and water afford two 3D-diamond-like networks, (CN(4)-C(6)H(5))(2)Zn (1) and (NH(2)-C(5)H(3)N-CN(4))(2)Zn (2), and one 2D square grid network, [(CN(4)-C(6)H(4)-C(12)H(7)N-C(5)H(4)N)(2)Zn].1.5H(2)O (3), in which these ligands gradually involve a noncenter-A-D (acceptor-donor) system, a one-center-A-D system, and a two-center-A-D system, respectively. All three compounds crystallize in noncentrosymmetric space groups (I2d for 1 and 2 and Fdd2 for 3) and display strong second harmonic generation (SHG) responses. Among the three new complexes, 3 shows the largest SHG effect, which is about 50 and 500 times that of urea and KDP (KH(2)PO(4)), respectively. The two-center-A-D system (multicenter push-pull electronic effect) in 3 may be responsible for it having the largest SHG effect. Interestingly, the three compounds exhibit strong fluorescent emissions at different wavelengths, 1 and 2 with blue fluorescent emissions at 390 and 415 nm and 3 with yellow-green fluorescent emissions at 495 and 532 nm.

The first metal (Nd3+, Mn2+, and Pb2+) coordination compounds of 3,5-dinitrotyrosine and their nonlinear optical properties.

The reactions of 3,5-dinitrotyrosine (H2DNTY) with Nd(NO3)3.6H2O, Mn(ClO4)2.6H2O, and Pb(OAc)2 afforded three homochiral compounds: discrete [Nd(Hdnty)2(NO3)(H2O)5].3H2O (1) and two- and three-dimensional coordination polymers, [Mn(Hdnty)2] (2) and [Pb(dnty)(0.5 H2O)] (3), respectively. The Nd atom in 1 displays a tricapped trigonal prism and supramolecular weak interactions, such as pi-pi stacking and H-bonds, between amino and nitro groups result in the formation of a three-dimensional network through these interactions. 2 has a two-dimensional square-grid topological net while 3 has the first three-dimensional homochiral ThSi2 net. To the best of our knowledge, these are the first metal coordination compounds with 3,5-dinitrotyrosine. Preliminary second harmonic generation (SHG) investigations indicated that 1 and 2 are SHG active with estimated responses 5 and 6 times larger than that of urea, respectively, while 3 is SHG non-active (obeying the Klainman symmetry requirement). Strong enhancement of their SHG efficiency, compared with H2DNTY, may be due to 1) the addition of a good donor-pi-acceptor organic chromophore into the compound resulting in superior qualities of both inorganic and organic materials and 2) the H-bonds that persist in them. Crystal data: 1: C18H32N7O25Nd, Mr = 890.75 g mol(-1), monoclinic, P2(1), a=7.0179(7), b=27.060(3), c=8.3097(8) A, alpha=gamma=90.00, beta=95.646(2) degrees , V=1570.4(3) A(3), Z=2, rho(calcd)=1.884 Mg m(-3), R(1)=0.0489, wR(2)=0.1223, mu=17.67 mm(-1), S=0.811, Flack value=0.003(13); 2: C(18)H(16)N(6)O(14)Mn, M(r)=595.31 g mol(-1), orthorhombic, P2(1)2(1)2, a=8.4381(14), b=13.639(2), c=19.697(3) A, alpha=beta=gamma=90.00 degrees , V=2266.9(6) A(3), Z=4, rho(calcd)=1.744 Mg m(-3), R(1)=0.0866, wR(2)=0.2030, mu=6.72 mm(-1), S=1.095, Flack value=0.02(6); 3: C(9)H(8)N(3)O(7.5)Pb, M(r)=485.37 g mol(-1), tetragonal, P4(1)2(1)2, a=12.8136(12), b=12.8136(12), c=14.931(2), alpha=beta=gamma=90.00 degrees , V=2451.5(5) A(3), Z=8, rho(calcd)=1.885 Mg m(-3), R(1)=0.0564, wR(2)=0.1323, mu=6.942 mm(-1), S=0.878, Flack value=0.03(2). For space group P4(3)2(1)2: R(1)=0.0672, wR(2)=0.1656, S=1.034, Flack value=1.02(3); this suggests the chosen space group P4(1)2(1)2 is correct.

Homochiral Zn and Cd coordination polymers containing amino acid-tetrazole ligands.

The reactions of (S)-3-cyanophenylalanine with NaN(3) in the presence of H(2)O and Lewis acids (ZnCl(2) and CdCl(2)) afford two unprecedented 3D homochiral networks, mono[(S)-5-(3-tetrazoyl)-phenylalaninato]zinc(II) (1) and mono[(S)-5-(3-tetrazoyl)-phenylalaninato]cadmium(II) monoaqua(II) (2), respectively. The two compounds are isostructural with noninterpenetrated SrAl(2) topology. The structure of these coordination polymers gives new insight into Sharpless' reaction of chiral 5-substituted 1H-tetrazole and homochiral supramolecular array constructions.