Determination of estrogenic steroids in surface water and wastewater by liquid chromatography-electrospray tandem mass spectrometry

An analytical method is presented which permits trace level determination of 17alpha-ethynylestradiol (EE2), 17beta-estradiol (E2), and estrone (E1). Using this method, the estrogenic steroids were analyzed in drinking water, surface water, and wastewater (sewage influents and effluents) at concentrations down to 0.1 ng/L. Sample volumes between 100 and 500 mL are concentrated using automated solid-phase extraction. Analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Applying simple clean-up procedures and internal standard calibration, recovery losses resulting from matrix-dependent ion suppression during electrospray ionization could be compensated for all of the investigated compounds. Recoveries around 100% were obtained for all analytes after correction using the internal standards. Limits of quantification (LOQ) were between 0.1 and 0.4 ng/L for purified sewage, surface, ground, and drinking water and between 1 and 2 ng/L in the case of raw sewage. Water treatment by wastewater treatment plants (WWTPs) or by a surface water treatment plant affected the removal of all estrogenic steroids. Thus, E1, E2, and EE2 were removed in the municipal WWTPs to the extent of 93%, 93%, and 80%, respectively. In the effluents of the WWTP in Ruhleben (Berlin, Germany), E1, E2, and EE2 were detected at the low ng/L level. E2 and EE2 were, however, not present in the Berlin surface water above the LOQ (0.2 ng/L). E1 was the only compound that could be detected in surface water samples. After additional surface water treatment it was still detectable but only at trace-level concentrations with a mean value of 0.16 ng/L.     

Long-time overdamped Langevin dynamics of molecular chains

We present a novel algorithm of constrained, overdamped dynamics to study the long-time properties of peptides, proteins, and related molecules. The constraints are applied to an all-atom model of the molecule by projecting out all components of the nonbonding interactions which tend to alter fixed bond lengths and angles. Because the overdamped dynamical equations are first order in time, the constraints are satisfied by inversion of a banded matrix at each timestep, which is computationally efficient. Thermal effects are included through a Langevin noise term in the equation of motion. Because high-frequency components of the motion have been eliminated, the timestep of the algorithm is determined by the nonbonding forces, which are two to three orders of magnitude weaker than the bonding forces. Using polyalanine as a test example, we demonstrate that trajectories simulating a microsecond of motion can be run about 10³ times faster than an equivalent molecular dynamics simulation. © 1994 by John Wiley & Sons, Inc.     

Sensitized photoconduction in a polydiacetylene crystal (DCHD)

The photoconductivity of DCHD displays a maximum near 3.6 eV coinciding with the maximum of the S_o → S₁ absorption of the carbazole group. It is attributed to a sensitization involving charge transfer from the excited chromophore to the chain. The rate constant for non-radiative decay of the carbazole singlet due to energy transfer to the chain is 1.6 × 10¹³ s^?1, and for charge transfer ≈ 3 × 10¹¹ s^?1.     

Recent advances in the synthesis of well-defined glycopolymers

Glycopolymers are receiving increasing interest due to their application in areas, such as glycomics, medicine, biotechnology, sensors, and separation science. Consequently, new methods for their synthesis are constantly being developed, with an increasing emphasis on the preparation of well-defined polymers and on the production of complex macromolecular architectures such as stars. This review covers recent developments in the synthesis of glycopolymers, with a particular emphasis on (i) the use of controlled radical polymerization to prepare well-defined glycopolymers from unprotected monomers and (ii) postpolymerization modification strategies using reactive polymer precursors (including “click” reactions). Recent work on the production of glycosylated polypeptides, which are under investigation as mimics of naturally occurring glycoproteins, is also included. The authors offer some suggestions as to future developments and remaining challenges in this topical area of polymer chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem45: 2059–2072, 2007     

Hierarchical assembly of helicate-type dinuclear titanium(IV) complexes

The ligands 4-7-H(2) were used in coordination studies with titanium(IV) and gallium(III) ions to obtain dimeric complexes Li(4)[(4-7)(6)Ti(2)] and Li(6)[(4/5a)(6)Ga(2)]. The X-ray crystal structures of Li(4)[(4)(6)Ti(2)], Li(4)[(5b)(6)Ti(2)], and Li(4)[(7a)(6)Ti(2)] could be obtained. While these complexes are triply lithium-bridged dimers in the solid state, a monomer/dimer equilibrium is observed in solution by NMR spectroscopy and ESI FT-ICR MS. The stability of the dimer is enhanced by high negative charges (Ti(IV) versus Ga(III)) of the monomers, when the carbonyl units are good donors (aldehydes versus ketones and esters), when the solvent does not efficiently solvate the bridging lithium ions (DMSO versus acetone), and when sterical hindrance is minimized (methyl versus primary and secondary carbon substituents). The dimer is thermodynamically favored by enthalpy as well as entropy. ESI FT-ICR mass spectrometry provides detailed insight into the mechanisms with which monomeric triscatecholate complexes as well as single catechol ligands exchange in the dimers. Tandem mass spectrometric experiments in the gas phase show the dimers to decompose either in a symmetric (Ti) or in an unsymmetric (Ga) fashion when collisionally activated. The differences between the Ti and Ga complexes can be attributed to different electronic properties and a charge-controlled reactivity of the ions in the gas phase. The complexes represent an excellent example for hierarchical self-assembly, in which two different noncovalent interactions of well balanced strengths bring together eleven individual components into one well-defined aggregate.     

Synthese und Charakterisierung neuer intramolekular stickstoffstabilisierter Organoaluminium‐ und Organogalliumalkoxide

Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me₂Al{μ‐O(CH₂)₃NMe₂}]₂ ( 1a ), Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6 ( 2a ), [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]₂ ( 3a ) and [(S)‐Me₂Al{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]₂ ( 4 ) are formed by reacting equimolar amounts of AlMe₃ and Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH₂OH, or (S)‐PhCH₂NHCH(i‐Pr)CH₂OH, respectively. An excess of AlMe₃ reacts with Me₂N(CH₂)₂OH, Me₂N(CH₂)₃OH, C₆H₂[(CH₂NMe₂)₃‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH₂OH producing the “pick‐a‐back” complexes [Me₂AlO(CH₂)₂NMe₂](AlMe₃) ( 5 ), [Me₂AlO(CH₂)₃NMe₂](AlMe₃) ( 1b ), [Me₂AlOC₆H₂(CH₂NMe₂)₃‐2,4,6](AlMe₃)₂ ( 2b ), and [(S)‐Me₂AlOCH₂CH(i‐Pr)NH‐i‐Pr](AlMe₃) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 6 ) and [{CH₂=C(CH₃)}(Cl)Al{μ‐O(CH₂)₂NMe₂}]₂ ( 8 ) are to obtain from Me₂AlCl and Me₂N(CH₂)₂OH and from [Cl₂Al{μ‐O(CH₂)₂NMe₂}]₂ ( 7 ) and CH₂=C(CH₃)MgBr, respectively. The analogous dimethylgallium alkoxides [Me₂Ga{μ‐O(CH₂)₃NMe₂}]₂ ( 9 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NH‐i‐Pr}]_n ( 10 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)NHCH₂Ph}]_n ( 11 ), [(S)‐Me₂Ga{μ‐OCH₂CH(i‐Pr)N(Me)CH₂Ph}]_n ( 12 ) and [(S)‐Me₂Ga{μ‐OCH₂(C₄H₇NHCH₂Ph)}]_n ( 13 ) result from the equimolar reactions of GaMe₃ with the corresponding alcohols. The new compounds were characterized by elemental analyses, ¹H‐, ¹³C‐ and ²⁷Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction.     

Macrophage-targeting oligopeptides from Mortierella alpina

The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.

Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages.     

Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.