Comparison of different approaches for direct coupling of solid-phase microextraction to mass spectrometry for drugs of abuse analysis in plasma

The direct coupling of solid-phase microextraction(SPME)to mass spectrometry(MS)(SPME-MS)has proven to be an effective method for the fast screening and quantitative analysis of compounds in complex matrices such as blood and plasma.In recent years,our lab has developed three novel SPME-MS techniques:SPME-microfluidic open interface-MS(SPME-MOI-MS),coated blade spray-MS(CBS-MS),and SPME-probe electrospray ionization-MS(SPME-PESI-MS).The fast and high-throughput nature of these SPME-MS technologies makes them attractive options for point-of-care analysis and anti-doping testing.However,all these three techniques utilize different SPME geometries and were tested with different MS instruments.Lack of comparative data makes it difficult to determine which of these methodologies is the best option for any given application.This work fills this gap by making a comprehensive comparison of these three technologies with different SPME devices including SPME fibers,CBS blades,and SPME-PESI probes and SPME-liquid chromatography-MS(SPME-LC-MS)for the analysis of drugs of abuse using the same MS instrument.Furthermore,for the first time,we developed different desorption chambers for MOI-MS for coupling with SPME fibers,CBS blades,and SPME-PESI probes,thus illustrating the universality of this approach.In total,eight analytical methods were developed,with the experimental data showing that all the SPME-based methods provided good analytical performance with R^(2)of linearities larger than 0.9925,accuracies between 81%and 118%,and good precision with an RSD%≤13%.

Biopolymer passivation for high-performance perovskite solar cells by blade coating

Thin films of perovskite deposited from solution inevitably introduce large number of defects,which serve as recombination centers and are detrimental for solar cell performance.Although many small molecules and polymers have been delicately designed to migrate defects of perovskite films,exploiting credible passivation agents based on natural materials would offer an alternative approach.Here,an ecofriendly and cost-effective biomaterial,ploy-L-lysine(PLL),is identified to effectively passivate the defects of perovskite films prepared by blade-coating.It is found that incorporation of a small amount(2.5 mg mL^(-1))of PLL significantly boosts the performance of printed devices,yielding a high efficiency of 19.45% with an increase in open-circuit voltage by up to 100 mV.Density functional theory calculations combined with X-ray photoelectron spectroscopy reveal that the functional groups(-NH2,-COOH)of PLL effectively migrate the Pb-I antisite defects via Pb-N coordination and suppress the formation of metallic Pb in the blade-coated perovskite film.This work suggests a viable avenue to exploit passivation agents from natural materials for preparation of high-quality perovskite layers for optoelectronic applications.

Hyperbranched phthalocyanine enabling black-phase formamidinium perovskite solar cells processing and operating in humidity open air

The extreme instability of pureα-phase FAPbI_(3) under high humidity conditions restricts the highthroughput fabrication in unmodified air environments,resulting in poor performance ofα-phase FAPbI_(3) perovskite devices obtained by scalable fabrication methods.Here we synthesized hyperbranched copper phthalocyanine(HCuPc)as a supramolecular additive with twisted phthalocyanine units to realize the molecular-level encapsulation at the grain boundaries through supramolecular interaction,which greatly broadened the processing window of FAPbI_(3) under high humidity.At the same time,unlike traditional encapsulation layer that carrier can only be collected by tunneling effect,the twisted phthalocyanine ring of HCu Pc in perovskite films is more conducive to hole extraction.Finally,a record efficiency was achieved in pure FAPbI_(3) based inverted structured solar cell by blade-coating to the best of our knowledge,even under unmodified humid air conditions(relative humidity of 65%–85%).The best operational stability of 3D pure FAPbI_(3) devices can also be achieved at the same time and unencapsulated HCuPc-FAPbI_(3) device can even operate with negligible degradation for 100 h in the open air(RH 30%–40%).

Time-course monitoring of in vitro biotransformation reaction via solid-phase microextraction-ambient mass spectrometry approaches

The solid-phase microextraction technique quantifies analytes without considerably affecting the sample composition.Herein,a proof-of-concept study was conducted to demonstrate the use of coated probe electrospray ionization(coated-PESI)and coated blade spray(CBS)as ambient mass spectrometry approaches for monitoring drug biotransformation.The ability of these methods was investigated for monitoring the dephosphorylation of a prodrug,combretastatin A4 phosphate(CA4P),into its active form,combretastatin A4(CA4),in a cell culture medium supplemented with fetal bovine serum.The CBS spot analysis was modified to achieve the same extraction efficiency as protein precipitation and obtained results in 7 min.Because coated-PESI performs extraction without consuming any samples,it is the preferred technique in the case of a limited sample volume.Although coated-PESI only extracts small quantities of analytes,it uses the desorption solvent volume of 5-10 pL,resulting in high sensitivity,thus allowing the detection of compounds after only 1 min of extraction.The biotransformation of CA4P into CA4 via phosphatases occurs within the simple matrix,and the proposed sample preparation techniques are suitable for monitoring the biotransformation.

Highly oriented MXene/polyvinyl alcohol films prepared by scalable layer-by-layer blade coating for efficient electromagnetic interference shielding and infrared stealth

Controlling the orientation of two-dimensional MXene within layered films is essential to optimize or tune their mechanical properties and electromagnetic interference shielding(EMI)performance,but achieving the high orientation MXene layers on an industrial scale remains a challenging goal.In this paper,a scalable layer-by-layer blade coating(LbLBC)method was employed to fabricate highly oriented MXene/polyvinyl alcohol(PVA)films.During the LbLBC process,MXene/PVA colloid suffered a strong shearing effect,which induced the ordered alignment of MXene nanosheets along the direction of the blade movement.The orientation of MXene can be effectively adjusted by changing the scraping gap of LbLBC,achieving a maximum Herman orientation factor f of 0.81.As a result,the mechanical properties and EMI performance of the as-prepared MXene/PVA films are in direct proportion to their orientation,with the optimal values of tensile strength of 145.5 MPa,fracture strain of 19.6%,toughness of 17.7 MJ·m^(−3),and EMI shielding effectiveness of 36.7 dB.Furthermore,the inherently low mid-infrared(mid-IR)emissivity of MXene,combined with the densely oriented structure affords the composite films with IR stealth,resulting in a substantial decrease from 150 to 66.1℃in the radiative temperature of a surface.Conclusively,these scalable MXene/PVA films exhibit remarkable potential for integration into the next generation of multifunctional protective camouflage materials.

Efficient fully blade-coated perovskite solar cells in air with nanometer-thick bathocuproine buffer layer

Fully printed perovskite solar cells(PSCs)were fabricated in air with all constituent layers,except for electrodes,deposited by the blade coating technique.The PSCs incorporated,for the first time,a nanometer-thick printed bathocuproine(BCP)hole blocking buffer using blade coating and deposited at relative humidity up to 50%.The PSCs with a p-i-n structure(glass/indium tin oxide(ITO)/poly(3,4-ethylenedioxythiophene)polystyrene sulfonate(PEDOT:PSS)/CH_(3)NH_(3)Pbl_(3)/[6,6]-phenyl-C_(61)-butyric acid methyl ester(PCBM)/BCP/Ag)delivered a maximum power conversion efficiency(PCE)of 14.9%on an active area of 0.5 cm^(2)when measured under standard test conditions.The PSCs with a blade coated BCP delivered performance of 10%and 63%higher(in relative terms)than those incorporating a spin coated BCP or without any BCP film,respectively.The atomic force microscopy(AFM)showed that blade coated films were more homogeneous and acted also as a surface planarizer leading to a reduction of roughness which improved BCP/Ag interface lowering charge recombination.The demonstration of 15%efficient devices with all constituent layers,including nanometer-thick BCP(〜10 nm),deposited by blade coating in air,demonstrates a route for industrialization of this technology.

Stable PbS colloidal quantum dot inks enable blade‑coating infrared solar cells

Infrared solar cells are more efective than normal bandgap solar cells at reducing the spectral loss in the near-infrared region,thus also at broadening the absorption spectra and improving power conversion efciency.PbS colloidal quantum dots(QDs)with tunable bandgap are ideal infrared photovoltaic materials.However,QD solar cell production sufers from small-areabased spin-coating fabrication methods and unstable QD ink.Herein,the QD ink stability mechanism was fully investigated according to Lewis acid–base theory and colloid stability theory.We further studied a mixed solvent system using dimethylformamide and butylamine,compatible with the scalable manufacture of method-blade coating.Based on the ink system,100 cm2 of uniform and dense near-infrared PbS QDs(~0.96 eV)flm was successfully prepared by blade coating.The average efciencies of above absorber-based devices reached 11.14%under AM1.5G illumination,and the 800 nm-fltered efciency achieved 4.28%.Both were the top values among blade coating method based devices.The newly developed ink showed excellent stability,and the device performance based on the ink stored for 7 h was similar to that of fresh ink.The matched solvent system for stable PbS QD ink represents a crucial step toward large area blade coating photoelectric devices.

Free vibration analysis of a pre-twisted sandwich blade with thermal barrier coatings layers

A rotating cantilever sandwich-plate model with a pre-twisted and pre-set angle has been developed to investigate the vibrational behavior of an aero-engine turbine blade with thermal barrier coating(TBC) layers. The classic von Karman plate theory and the first-order shear deformation theory are applied to derive the energy equations of the rotating TBC blade, in which the geometric shapes, the work ambient temperature, and the TBC material properties are considered. The Chebyshev-Ritz method is used to obtain the nature frequency of the rotating TBC blade. For static frequency and modal analysis, the finite-element method(FEM)is also applied to compare and validate the results from the Chebyshev-Ritz method. A good agreement is found among these kinds of methods. For dynamic frequency, the results are analyzed in detail concerning the influence of system parameters such as the thickness of the TBC layer, the working temperature, and the pre-twisted and pre-set angle. Finally, the Campbell diagram is demonstrated to analyze the resonance property of the cantilever sandwich TBC blade model.

A Solution Processable Flexible Transparent Conductive Graphene/PEDOT : PSS Film Fabricated by Spin and Blade Coating

Flexible transparent conductive films were made on PET substrates by spin and blade coating, using graphene sheets dispersed in PEDOT : PSS solution. Ultrasonic substrate vibration was used to improve microstructure and properties of the films. Comparing to the pristine PEDOT : PSS film, the sheet resistance is 3 to 4 orders of magnitude lower with the addition of graphene. The conductivity and reproducibility of the film are improved for two-layer films comparing to one-layer films, with a reduction in transparency. Films prepared with substrate vibration showed lower sheet resistance for one-layer films, as the size of dewetting areas is reduced. In addition, large-area flexible films with desirable conductivity and transmittance were successfully fabricated by blade coating, which is promising, as the process is low-cost, scalable and compatible with roll-to-roll manufacturing.

Conjugate Heat Transfer Investigation on the Cooling Performance of Air Cooled Turbine Blade with Thermal Barrier Coating

A hot wind tunnel of annular cascade test rig is established for measuring temperature distribution on a real gas turbine blade surface with infrared camera.Besides,conjugate heat transfer numerical simulation is performed to obtain cooling efficiency distribution on both blade substrate surface and coating surface for comparison.The effect of thermal barrier coating on the overall cooling performance for blades is compared under varied mass flow rate of coolant,and spatial difference is also discussed.Results indicate that the cooling efficiency in the leading edge and trailing edge areas of the blade is the lowest.The cooling performance is not only influenced by the internal cooling structures layout inside the blade but also by the flow condition of the mainstream in the external cascade path.Thermal barrier effects of the coating vary at different regions of the blade surface,where higher internal cooling performance exists,more effective the thermal barrier will be,which means the thermal protection effect of coatings is remarkable in these regions.At the designed mass flow ratio condition,the cooling efficiency on the pressure side varies by 0.13 for the coating surface and substrate surface,while this value is 0.09 on the suction side.