2,3‐Di(2‐pyridyl)‐5‐phenylpyrazine: A NN‐CNN‐Type Bridging Ligand for Dinuclear Transition‐Metal Complexes

A new bridging ligand, 2,3‐di(2‐pyridyl)‐5‐phenylpyrazine (dpppzH), has been synthesized. This ligand was designed so that it could bind two metals through a NN‐CNN‐type coordination mode. The reaction of dpppzH with cis‐[(bpy)₂RuCl₂] (bpy=2,2′‐bipyridine) affords monoruthenium complex [(bpy)₂Ru(dpppzH)]²⁺ ( 12+ ) in 64 % yield, in which dpppzH behaves as a NN bidentate ligand. The asymmetric biruthenium complex [(bpy)₂Ru(dpppz)Ru(Mebip)]³⁺ ( 23+ ) was prepared from complex 12+ and [(Mebip)RuCl₃] (Mebip=bis(N‐methylbenzimidazolyl)pyridine), in which one hydrogen atom on the phenyl ring of dpppzH is lost and the bridging ligand binds to the second ruthenium atom in a CNN tridentate fashion. In addition, the RuPt heterobimetallic complex [(bpy)₂Ru(dpppz)Pt(C?CPh)]²⁺ ( 42+ ) has been prepared from complex 12+ , in which the bridging ligand binds to the platinum atom through a CNN binding mode. The electronic properties of these complexes have been probed by using electrochemical and spectroscopic techniques and studied by theoretical calculations. Complex 12+ is emissive at room temperature, with an emission λ_max=695 nm. No emission was detected for complex 23+ at room temperature in MeCN, whereas complex 42+ displayed an emission at about 750 nm. The emission properties of these complexes are compared to those of previously reported Ru and RuPt bimetallic complexes with a related ligand, 2,3‐di(2‐pyridyl)‐5,6‐diphenylpyrazine.     

New Dual Donor–Acceptor (2D‐π‐2A) Porphyrin Sensitizers for Stable and Cost‐Effective Dye‐Sensitized Solar Cells

A series of porphyrin sensitizers that featured two electron‐donating groups and dual anchoring groups that were connected through a porphine π‐bridging unit have been synthesized and successfully applied in dye‐sensitized solar cells (DSSCs). The presence of electron‐donating groups had a significant influence on their spectroscopic, electrochemical, and photovoltaic properties. Overall, the dual anchoring groups gave tunable electronic properties and stronger attachment to TiO₂. These new dyes were readily synthesized in a minimum number of steps in gram‐scale quantities. Optical and electrochemical data confirmed the advantages of these dyes for use as sensitizers in DSSCs. Porphyrins with electron‐donating amino moieties provided improved charge separation and better charge‐injection efficiencies for the studied dual‐push–pull dyes. Attenuated total reflectance–Fourier‐transform infrared (ATR‐FTIR) and X‐ray photoelectron spectroscopy of the porphyrin dyes on TiO₂ suggest that both p‐carboxyphenyl groups are attached onto TiO₂, thereby resulting in strong attachment. Among these dyes, cis-Zn2BC2A , with two electron‐donating 3,6‐ditertbutyl‐phenyl‐carbazole groups and dual‐anchoring p‐carboxyphenyl groups, showed the highest efficiency of 4.07 %, with J_SC=9.81 mA cm^?2, V_OC=0.63 V, and FF=66 %. Our results also indicated a better photostability of the studied dual‐anchored sensitizers compared to their mono‐anchored analogues under identical conditions. These results provide insight into the developments of a new generation of high‐efficiency and thermally stable porphyrin sensitizers.     

Adsorption of Polycyclic Aromatic Hydrocarbons on Graphene Oxides and Reduced Graphene Oxides

Graphene has attracted increasing attention in multidisciplinary studies because of its unique physical and chemical properties. Herein, the adsorption of polycyclic aromatic hydrocarbons (PAHs), such as naphthalene (NAP), anthracene (ANT), and pyrene (PYR), on reduced graphene oxides (rGOs) and graphene oxides (GOs) as a function of pH, humic acid (HA), and temperature were elucidated by means of a batch technique. For comparison, nonpolar and nonporous graphite were also employed in this study. The increasing of pH from 2 to 11 did not influence the adsorption of PAHs on rGOs, whereas the suppressed adsorption of NAP on rGOs was observed both in the presence of HA and under high‐temperature conditions. Adsorption isotherms of PAHs on rGOs were in accordance with the Polanyi–Dubinin–Ashtahhov (PDA) model, providing evidence that pore filling and flat surface adsorption were involved. The saturated adsorbed capacities (in mmol g^?1) of rGOs for PAHs calculated from the PDA model significantly decreased in the order of NAP>PYR>ANT, which was comparable to the results of theoretical calculations. The pore‐filling mechanism dominates the adsorption of NAP on rGOs, but the adsorption mechanisms of ANT and PYR on rGOs are flat surface adsorption.     

ZnII and CuII complexes generated from 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione

A new 1,3,4‐oxadiazole‐containing bispyridyl ligand, namely 5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione (L), has been used to create the novel complexes tetranitratobis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}zinc(II), [Zn₂(NO₃)₄(C₁₄H₁₂N₄OS)₂], (I), and catena‐poly[[[dinitratocopper(II)]‐bis{μ‐5‐(pyridin‐4‐yl)‐3‐[2‐(pyridin‐4‐yl)ethyl]‐1,3,4‐oxadiazole‐2(3H)‐thione}] nitrate acetonitrile sesquisolvate dichloromethane sesquisolvate], {[Cu(NO₃)(C₁₄H₁₂N₄OS)₂]NO₃·1.5CH₃CN·1.5CH₂Cl₂}_n, (II). Compound (I) presents a distorted rectangular centrosymmetric Zn₂L₂ ring (dimensions 9.56 × 7.06 Å), where each Zn^II centre lies in a {ZnN₂O₄} coordination environment. These binuclear zinc metallocycles are linked into a two‐dimensional network through nonclassical C—H...O hydrogen bonds. The resulting sheets lie parallel to the ac plane. Compound (II), which crystallizes as a nonmerohedral twin, is a coordination polymer with double chains of Cu^II centres linked by bridging L ligands, propagating parallel to the crystallographic a axis. The Cu^II centres adopt a distorted square‐pyramidal CuN₄O coordination environment with apical O atoms. The chains in (II) are interlinked via two kinds of π–π stacking interactions along [01]. In addition, the structure of (II) contains channels parallel to the crystallographic a direction. The guest components in these channels consist of dichloromethane and acetonitrile solvent molecules and uncoordinated nitrate anions.     

Porous V2O5-SnO2/CNTs composites as high performance cathode materials for lithium-ion batteries

Vanadium pentoxide (V₂O₅) exhibits high theoretical capacities when used as a cathode in lithium ion batteries (LIBs), but its application is limited by its structural instability as well as its low lithium and electronic conductivities. A porous composite of V₂O₅-SnO₂/carbon nanotubes (CNTs) was prepared by a hydrothermal method and followed by thermal treatment. The small particles of V₂O₅, their porous structure and the coexistence of SnO₂ and CNTs can all facilitate the diffusion rates of the electrons and lithium ions. Electrochemical impedance spectra indicated higher ionic and electric conductivities, as compared to commercial V₂O₅. The V₂O₅-SnO₂/CNTs composite gave a reversible discharge capacity of 198 mAh·g^?1 at the voltage range of 2.05–4.0 V, measured at a current rate of 200 mA·g^?1, while that of the commercial V₂O₅ was only 88 mAh·g^?1, demonstrating that the porous V₂O₅-SnO₂/CNTs composite is a promising candidate for high-performance lithium secondary batteries.     

Development of a rapid method for the simultaneous separation and determination of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol and its N- and O-glucuronides in human urine by liquid chromatography–tandem mass spectrometry

Determination of the tobacco-specific nitrosamine metabolite 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) and its N- and O-glucuronides (NNAL-N-Gluc and NNAL-O-Gluc) is important for toxicology analysis of tobacco smoke induced carcinogenicity and the understanding of detoxification mechanisms of the carcinogenic nitrosamine in humans. But previously reported indirect measurement methods involving enzymolysis and base treatment steps were tedious and time-consuming. In this work, a direct measurement method for simultaneous determination of urinary NNAL, NNAL-N-Gluc and NNAL-O-Gluc by liquid chromatography–tandem mass spectrometry (LC–MS/MS) in a single run was developed for the first time without the need to perform enzymatic or base hydrolysis. Urine samples were purified using dichloromethane and further extracted by solid-phase extraction. Then they were analyzed by LC–MS/MS operated in electrospray positive ionization mode. Chromatographic separation was achieved on a Phenomenex Kinetex PFP column within 6 min. The proposed method was validated and the results demonstrated that the method can produce satisfactory recoveries and reproducibility for the analytes. The applicability of this newly developed method was investigated for the simultaneous analysis of the three metabolites in smokers’ urine and the obtained results were comparable to those detected using the conventional enzymolysis method.     

Sensitive detection of human breast cancer cells based on aptamer–cell–aptamer sandwich architecture

Breast cancer is one of the most critical threats to the health of women, and the development of new methods for early diagnosis is urgently required, so this paper reports a method to detect Michigan cancer foundation-7 (MCF-7) human breast cancer cells with considerable sensitivity and selectivity by using electrochemical technique. In this method, a mucin 1 (MUC1)-binding aptamer is adopted to recognize MCF-7 human breast cancer cells, while enzyme labeling is employed to produce amplified catalytic signals. The molecular recognition and the signal amplification are elaborately integrated by fabricating an aptamer–cell–aptamer sandwich architecture on an electrode surface, thus a biosensor for the detection of MCF-7 is fabricated based on the architecture. The detection range can be from 100 to 1 × 10⁷ cells, and the detection limit can be as low as 100 cells. The method is also cost-effective and conveniently operated, implying potential help for the development of early diagnosis of breast cancer.     

Hyphenation of optimized microfluidic sample preparation with nano liquid chromatography for faster and greener alkaloid analysis

A glass liquid–liquid extraction (LLE) microchip with three parallel 3.5 cm long and 100 μm wide interconnecting channels was optimized in terms of more environmentally friendly (greener) solvents and extraction efficiency. In addition, the optimized chip was successfully hyphenated with nano-liquid chromatography with ultraviolet and mass spectrometric detection (nanoLC–UV–MS) for on-line analysis. In this system, sample pretreatment, separation and detection are integrated, which significantly shortens the analysis time, saves labor and drastically reduces solvent consumption. Strychnine was used as model analyte to determine the extraction efficiency of the optimized 3-phase chip. Influence of organic solvent, pH of feed phase, type of alkaloid, and flow rates were investigated. The results demonstrated that the 3-phase chip nanoLC–UV/MS hyphenation combines rapid (∼25 s) and efficient (extraction efficiency >90%) sample prep, with automated alkaloid analyses. The method was applied to real samples including Strychnos nux-vomica seeds, Cephaelis ipecacuanha roots, Atropa belladonna leaves, and Vinca minor leaves.     

High sensitivity chemiluminescence enzyme immunoassay for detecting staphylococcal enterotoxin A in multi-matrices

In this study, detection of staphylococcal enterotoxin A (SEA) in multi-matrices using a highly sensitive and specific microplate chemiluminescence enzyme immunoassay (CLEIA) has been established. A pair of monoclonal antibodies (mAbs) was selected from 37 anti-SEA mAbs by pairwise analysis, and the experimental conditions of the CLEIA were optimized. This CLEIA exhibited high performance with a wide dynamic range from 6.4 pg mL⁻¹ to 1600 pg mL⁻¹, and the measured low limit of detection (LOD) was 3.2 pg mL⁻¹. No cross-reactivity was observed when this method was applied to test SEB, SEC1, and SED. It has also been successfully applied for analyzing SEA in a variety of environmental, biological, and clinical matrices, such as sewage, tap water, river water, roast beef, peanut butter, cured ham, 10% nonfat dry milk, milk, orange juice, human urine, and serum. Thus, the highly sensitive and SEA-specific CLEIA should make it attractive for quantifying SEA in public health and diagnosis in near future.     

Ultrasonic-Assisted Nebulization Extraction Coupled with SPE and HPLC for the Determination of Triterpenoids in Root of Euphorbia pekinensis Rupr.

In this work, a novel method based on ultrasonic-assisted nebulization extraction coupled with solid phase extraction (UANE-SPE) and determined by high performance liquid chromatography was developed for the determination of triterpenoids in root of Euphorbia pekinensis Rupr. The experimental conditions for the UANE-SPE, such as type of extraction solvent, sample amount, type and amount of sorbent, extraction time and volume of the elution solvent, were examined and optimized. The method was successfully applied to determine euphol and tirucallol in the dried root of E. pekinensis Rupr. The recoveries of the analytes were in the range of 89.1–102.0 %. The limits of detection were 12 μg g^?1 for tirucallol and 10 μg g^?1 for euphol. The extraction yields obtained by the proposed method are higher than those obtained by the conventional extraction methods, such as reflux and ultrasonic-assisted extraction. Compared with the traditional methods, the proposed method can reduce the consumption of the labor, shorten the sample preparation time and increase the efficiencies in the extraction of active constituents from plant materials.