Liquid chromatography–mass spectrometry applications for quantification of endogenous sex hormones

Liquid chromatography, coupled with tandem mass spectrometry, presents a powerful tool for the quantification of the sex steroid hormones 17‐β estradiol, progesterone and testosterone from biological matrices. The importance of accurate quantification with these hormones, even at endogenous levels, has evolved with our understanding of the role these regulators play in human development, fertility and disease risk and manifestation. Routine monitoring of these analytes can be accomplished by immunoassay techniques, which face limitations on specificity and sensitivity, or using gas chromatography–mass spectrometry. LC–MS/MS is growing in capability and acceptance for clinically relevant quantification of sex steroid hormones in biological matrices and is able to overcome many of the limitations of immunoassays. Analyte specificity has improved through the use of novel derivatizing agents, and sensitivity has been refined through the use of high‐resolution chromatography and mass spectrometric technology. This review highlights these innovations, among others, in LC–MS/MS steroid hormone analysis captured in the literature over the last decade.     

Solution-Based,Anion-Doping of Li4Ti5O12 Nanoflowers for Lithium-Ion Battery Applications

Solution-based, anionic doping represents a convenient strategy with which to improve upon the conductivity of candidate anode materials such as Li₄Ti₅O₁₂ (LTO). As such, novel synthetic hydrothermally-inspired protocols have primarily been devised herein, aimed at the large-scale production of unique halogen-doped, micron-scale, three-dimensional, hierarchical LTO flower-like motifs. Although fluorine (F) doping has been explored, the use of chlorine (Cl) dopants is the primary focus here. Several experimental variables, such as dopant amount, lithium hydroxide concentration, and titanium butoxide purity, were probed and perfected. Furthermore, the Cl doping process did not damage the intrinsic LTO morphology. The analysis, based on interpreting a compilation of SEM, XRD, XPS, and TEM-EDS results, was used to determine an optimized dopant concentration of Cl. Electrochemical tests demonstrated an increased capacity via cycling of 12 % for a Cl-doped sample as compared with pristine LTO. Moreover, the Cl-doped LTO sample described in this study exhibited the highest discharge capacity yet reported at an observed rate of 2C for this material at 143mAh g⁻¹. Overall, these data suggest that the Cl dopant likely enhances not only the ion transport capabilities, but also the overall electrical conductivity of our as-prepared structures. To help explain these favorable findings, theoretical DFT calculations were used to postulate that the electronic conductivity and Li diffusion were likely improved by the presence of increased Ti³⁺ ion concentration coupled with widening of the Li migration channel.     

Novel Copolymers of 4-Fluorostyrene. 1. Alkyl Ring-Substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, alkyl ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₄CH = C(CN)₂ (where R is 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-i-propyl, 4-butyl, 4-i-butyl, and 4-t-butyl) and 4-fluorostyrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r ₁) for the monomers is 4-ethyl (42.6) > 4-butyl (29.4) > 4-t-butyl (26.7) > 4-i-butyl (1.6) > 4-i-propyl (1.29) > 3-methyl (1.26) > 2-methyl (0.8) > 4-methyl (0.4). High T _g of the copolymers, in comparison with that of poly(4-fluorostyrene) indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in 183–500°C range with residue (5–30% wt.), which then decomposed in the 500–800°C range.     

Comparative pyrolysis upcycling of polystyrene waste: thermodynamics, kinetics, and product evolution profile

Pyrolysis is one important way to treat polystyrene waste and upcycle it into useful materials. A comparative pyrolysis study of virgin polystyrene (VPS) and two types of commonly used polystyrene products, expanded polystyrene (EPS) and polystyrene container (CPS) was carried out. Various values were found in the thermodynamic study and kinetic study of VPS, EPS, and CPS pyrolysis, suggesting distinct thermal degradation characteristics of these materials. The energy barrier order of the pyrolysis processes was EPS, CPS, VPS, showing activation energy of 230, 219, and 145 kJ mol^?1, respectively. The order of amount of heat absorbed was EPS, CPS, VPS, with enthalpy of 224, 213, and 139 kJ mol^?1, respectively. The reaction favorability order was EPS, CPS, and VPS with Gibbs free energy of 118, 132, and 210 kJ mol^?1, respectively. Thermogravimetric analysis indicated the use of high heating rate would increase the reaction rate and shorten the reaction time. Product evolution profiles showed that VPS and CPS pyrolysis produced mainly aromatics, while EPS pyrolysis produced aromatics at the initial phase of the reaction and aliphatic hydrocarbon at the latter phase. The diverse pyrolysis behaviors of VPS, EPS, and CPS demonstrated that an examination on different polystyrene materials was desired to optimize the pyrolysis conditions and product distribution, and thus benefit the process of valuable materials recovery.     

Embedded passivated-electrode insulator-based dielectrophoresis (EπDEP)

Here, we introduce a new technique called embedded passivated-electrode insulator-based dielectrophoresis (EπDEP) for preconcentration, separation, or enrichment of bioparticles, including living cells. This new method combines traditional electrode-based DEP and insulator-based DEP with the objective of enhancing the electric field strength and capture efficiency within the microfluidic channel while alleviating direct contact between the electrode and the fluid. The EπDEP chip contains embedded electrodes within the microfluidic channel covered by a thin passivation layer of only 4 μm. The channel was designed with two nonaligned vertical columns of insulated microposts (200 μm diameter, 50 μm spacing) located between the electrodes (600 μm wide, 600 μm horizontal spacing) to generate nonuniform electric field lines to concentrate cells while maintaining steady flow in the channel. The performance of the chip was demonstrated using Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacterial pathogens in aqueous media. Trapping efficiencies of 100 % were obtained for both pathogens at an applied AC voltage of 50 V peak-to-peak and flow rates as high as 10 μl/min.     

A Resin‐Linker‐Vector Approach to Radiopharmaceuticals Containing 18F: Application in the Synthesis of O‐(2‐[18F]‐Fluoroethyl)‐L‐tyrosine

A Resin‐linker‐vector (RLV) strategy is described for the radiosynthesis of tracer molecules containing the radionuclide ¹⁸F, which releases the labelled vector into solution upon nucleophilic substitution of a polystyrene‐bound arylsulfonate linker with [¹⁸F]‐fluoride ion. Three model linker‐vector molecules 7 a – c containing different alkyl spacer groups were assembled in solution from (4‐chlorosulfonylphenyl)alkanoate esters, exploiting a lipase‐catalysed chemoselective carboxylic ester hydrolysis in the presence of the sulfonate ester as a key step. The linker‐vector systems were attached to aminomethyl polystyrene resin through amide bond formation to give RLVs 8 a – c with acetate, butyrate and hexanoate spacers, which were characterised by using magic‐angle spinning (MAS) NMR spectroscopy. On fluoridolysis, the RLVs 8 a , b containing the longer spacers were shown to be more effective in the release of the fluorinated model vector (4‐fluorobutyl)phenylcarbamic acid tert‐butyl ester ( 9 ) in NMR kinetic studies and gave superior radiochemical yields (RCY≈60 %) of the ¹⁸F‐labelled vector. The approach was applied to the synthesis of the radiopharmaceutical O‐(2‐[¹⁸F]‐fluoroethyl)‐L ‐tyrosine ([¹⁸F]‐FET), delivering protected [¹⁸F]‐FET in >90 % RCY. Acid deprotection gave [¹⁸F]‐FET in an overall RCY of 41 % from the RLV.     

Three‐Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks

We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC⁴⁺) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC⁴⁺ rings comprise either 1) two bipyridinium (BIPY²⁺) units or 2) a BIPY²⁺ and a diazapyrenium (DAP²⁺) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO₃)₂?2.5 H₂O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY²⁺ units by a DAP²⁺ unit: only the translational isomer in which the DAP²⁺ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures.