Imparting Chemiresistor with Humidity-Independent Sensitivity toward Trace-Level Formaldehyde via Substitutional Doping Platinum Single Atom.

The modification of metal oxides with noble metals is one of the most effective means of improving gas-sensing performance of chemiresistors, but it is often accompanied by unintended side effects such as sensor resistance increases up to unmeasurable levels. Herein, a carbonization-oxidation method is demonstrated using ultrasonic spray pyrolysis technique to realize platinum (Pt) single atom (SA) substitutional doping into SnO2 (named PtSA-SnO2 ). The substitutional doping strategy can obviously enhance gas-sensing properties, and meanwhile decrease sensor resistance by two orders of magnitude (decreased from ≈850 to ≈2 MΩ), which are attributed to the tuning of band gap and fermi-level position, efficient single atom catalysis, and the raising of adsorption capability of formaldehyde, as validated by the state-of-the-art characterizations, such as spherical aberration-corrected scanning transmission electron microscopy (Cs -corrected STEM), in situ diffuse reflectance infrared Fourier transformed spectra (in situ DRIFT), CO temperature-programmed reduction (CO-TPR), and theoretical calculations. As a proof of concept, the developed PtSA-SnO2 sensor shows humidity-independent (30-70% relative humidity) gas-sensing performance in the selective detection of formaldehyde with high response, distinguishable selectivity (8< Sformaldehyde /Sinterferant <14), and ultra-low detection limit (10 ppb). This work presents a generalized and facile method to design high-performance metal oxides for chemical sensing of volatile organic compounds (VOCs).

Insights into Stereoselectivity Switch in Michael Addition-Initiated Tandem Mannich Cyclizations and Their Extension from Enamines to Vinyl Ethers.

Both cis- and trans- tetracyclic spiroindolines are the core of many important biologically active indole alkaloids, but the divergent synthesis of these important motifs is largely hampered by the limited stereoselectivity control. A facile stereoinversion protocol is reported here in Michael addition-initiated tandem Mannich cyclizations for constructing tetracyclic spiroindolines, providing an easy access to two diastereoisomeric cores of monoterpene indole alkaloids with high selectivity. The mechanistic studies including in situ NMR experiments, control experiments, and DFT calculations reveal that the reaction undergoes a unique retro-Mannich/re-Mannich rearrangement including a C-C bond cleavage that is very rare for a saturated six-membered carbocycle. Insights into the stereoinversion process have been uncovered, and the major effects were determined to be the electronic properties of N-protecting groups of the indole with the aid of Lewis acid catalysts. By understanding these insights, the stereoselectivity switching strategy is also smoothly applied from enamine substrates to vinyl ether substrates, which are enriched greatly for the divergent synthesis and stereocontrol of monoterpene indole alkaloids. The current reaction also proves to be very practical and was successfully applied to the gram-scale total synthesis of strychnine and deethylibophyllidine in short routes.

Allenamide-Initiated Cascade [2+2+2] Annulation Enabling the Divergent Total Synthesis of (-)-Deoxoapodine, (-)-Kopsifoline†D and (±)-Melotenine†A.

A facile method for the construction of the aspidosperma core from indoles functionalized with a nonterminal N-allenamide and dimethyl methylenemalonate is described. Various polysubstituted tetracyclic spiroindolines (27 examples) were afforded in good yields (61-90 %) with >99/1 dr and >99/1 Z/E selectivity under mild conditions. The annulation reaction provides straightforward access to the tetracyclic spiroindoline skeleton with substituents at the C5 position occurring in many natural products. As an application of this reaction, the total synthesis of three important natural products, (-)-deoxoapodine, (-)-kopsifoline D and (±)-melotenine A, was possible in short routes from tryptamine.

Selectivity Switch in a Rhodium(II) Carbene Triggered Cyclopentannulation: Divergent Access to Three Polycyclic Indolines.

A selectivity switch in a RhII /carbene-triggered cyclopentannulation with catalytic InCl3 is reported for the first time, affording both diastereomers of the fused spiroindolines and an unusual bridged tetracyclic indoline in high yields with excellent selectivities. Mechanistic studies indicate an intramolecular annulation of the indole with an in situ formed aminocyclopropane. The stepwise thermal conversions from the kinetic spiroindoline to the metastable bridged indoline, and then to the thermodynamic spiroindoline, involving a ring-opening rearrangement of a cyclopentane, is crucial for selectivity control.

Access to Hexahydrocarbazoles: The Thorpe-Ingold Effects of the Ligand on Enantioselectivity.

A novel cyclization reaction of methylenemalonate with indoles is reported, and it provides efficient access to a variety of hexahydrocarbazoles. The enantioselective version was realized by a finely tuned ligand/CuII catalyst. The optically active hexahydrocarbazoles contain three quaternary carbon centers and are obtained in up to 99 % yield with greater than 99:1 d.r. and up to greater than 99 % ee. This reaction can be carried out on gram scale and stereoselective transformation of the product led to the core structure of a series of alkaloids from Kopsia plants.

Enzymes on Steroids.

Efficient assembly and functionalization of biologically active steroids continue to pose a significant synthetic hurdle. The mining and engineering of selective P450 C-H hydroxylases combined with chemoenzymatic synthesis furnished a new solution to this challenging problem.

Wearable Gas Sensor Based on Reticular Antimony-Doped SnO2/PANI Nanocomposite Realizing Intelligent Detection of Ammonia within a Wide Range of Humidity.

Wearable gas sensors demonstrate broad potential for environmental monitoring and breath analysis applications. Typically, they require a highly stable and high-performance flexible gas sensing unit that can work with a small, flexible circuit to enable real-time accurate concentration analysis and prediction. This work proposes a flexible gas sensor using antimony-doped tin dioxide composite polyaniline as the sensing material for room-temperature ammonia detection over a wide humidity range. The sensor exhibits high sensitivity (response value at 33.1 toward 100 ppm ammonia at 70% relative humidity), excellent selectivity, and good long-term and mechanical stability. The increased sensitivity is due to a reduction in the hole concentration of polyaniline in air, achieved through compositing and doping. Subsequently, regression analysis equations are developed to establish the relationship between the gas concentration and sensor response under varying environmental humidity conditions. The sensor was integrated with a small, low-power circuit module to form a wearable smart bracelet with signal acquisition, processing, and wireless transmission functions, which could achieve early and remote warning of gas leakage in different humidity environments. This research demonstrates a promising approach to designing high-performance, high-stability, and flexible gas sensors and their corresponding wireless sensing systems.

Reply to the Comment on "Understanding the Increasing Trend of Sensor Signal with Decreasing Oxygen Partial Pressure by a Sensing-Reaction Model Based on O2- Species".

In our recent work (ACS Sens.2022, 7, 1095-1104), Mirabella et al. provided comments on our publication, mainly focusing on the controversy between the oxygen vacancy model and the ionosorbed model and the related derivation based on the law of mass action. Herein we explain the correlation between the ionosorption model and the oxygen vacancy model and provide a brief introduction of our view on these two models. Moreover, a more detailed derivation about the law of mass action is provided to explain the relationship between surface electron concentration, oxygen partial pressure, adsorbed oxygen density, and oxygen vacancy density.

All-Nanofiber Network Structure for Ultrasensitive Piezoresistive Pressure Sensors.

Sensing materials with fiber structures are excellent candidates for the fabrication of flexible pressure sensors due to their large specific surface area and abundant contact points. Here, an ultrathin, flexible piezoresistive pressure sensor that consists of a multilayer nanofiber network structure prepared via a simple electrospinning technique is reported. The ultrathin sensitive layer is composite nanofiber films composed of poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) and polyamide 6 (PEDOT:PSS/PA6) prepared by simultaneous electrospinning. PEDOT:PSS conductive fibers and PA6 elastic fibers are interwoven to form a multilayer network structure that can achieve ultrahigh sensitivity by forming a wealth of contact points during loading. In particular, gold-deposited PA6 fibers as upper and lower flexible electrodes can effectively increase the initial resistance. Due to this special fiber electrode structure, the sensor is able to generate a large electrical signal variability when subjected to a weak external force. The devices with different sensing properties can be obtained by controlling the electrospinning time. The sensor based on the PEDOT:PSS/PA6 nanofiber network has high sensitivity (6554.6 kPa-1 at 0-1.4 kPa), fast response time (53 ms), and wide detection range (0-60 kPa). Significantly, the device maintains ultrahigh sensitivity when cyclically loaded over 10,000 cycles at 5 kPa, which makes it have great prospects for applications in human health monitoring and motion monitoring.

Understanding the Increasing Trend of Sensor Signal with Decreasing Oxygen Partial Pressure by a Sensing-Reaction Model Based on O2- Species.

Although the increasing trend of sensor signal with decreasing oxygen partial pressure was observed quite early, the underlying mechanism is still elusive, which is a hindrance to accurate gas detection under varying oxygen partial pressure. In this work, a sensing model based on previous experimental and theoretical results is proposed, in which the O2- species is determined to be the main oxygen species because O- species has not been observed by direct spectroscopic studies. On this basis, combined with the band bending of SnO2 at different oxygen partial pressures, the functional relationship between the surface electron concentration, oxygen partial pressure, and reducing gas concentration is established, which includes three forms corresponding to the depletion layer, accumulation layer, and flat band. In the depletion layer case, the variation of the sensor resistance to different concentrations of CO and oxygen can be well fitted with our function model. Besides, this model predicts that the response of sensors will no longer maintain the increasing trend in an extremely hypoxic atmosphere but will decrease and approach 1 with the background oxygen content further going down to 0.

Multifunctional Flexible Ionic Skin with Dual-Modal Output Based on Fibrous Structure.

Flexible wearable electronic devices with multiple sensing functions that simulate human skin in all aspects have become a popular research topic. However, the current expensive and time-consuming means of integration and the complex decoupling process are hampering the further development of multifunctional sensors. Here, an ultraflexible ionic fiber membrane (IFM) prepared by a simple electrospinning technique is reported, which exhibits pressure and humidity sensing properties. With the help of different electrode structures, the IFM-based multifunctional sensor achieved pressure and humidity detection with different sensing mechanisms. Pressure sensing with high sensitivity (49.7 kPa-1 at 0-30 kPa) and wide detection range (0-220 kPa) was indicated by the capacitive signal. Humidity sensing with high linearity (1.086% per percent relative humidity (RH)) in the range 15%-90% RH was indicated by the resistance signal. In particular, the multimodal output of capacitance/resistance corresponding to pressure/humidity in this study directly addresses the problem of accurately distinguishing the two stimuli. Furthermore, we have demonstrated that the impact between pressure and humidity is negligible when measured simultaneously and independently. Because of the excellent pressure/humidity sensing performance, we have fabricated a smart bracelet and mask for pulse, skin moisture, and breathe monitoring, which indicates the promising future of multifunctional flexible sensors based on IFM in the healthcare field.

MOF-Derived Mesoporous and Hierarchical Hollow-Structured In2O3-NiO Composites for Enhanced Triethylamine Sensing.

It remains a challenge to design and fabricate high-performance gas sensors using metal-organic framework (MOF)-derived metal oxide semiconductors (MOS) as sensing materials due to the structural damage during the annealing process. In this study, the mesoporous In2O3-NiO hollow spheres consisting of nanosheets were prepared via a solvothermal reaction and subsequent cation exchange. More importantly, the transformation of Ni-MOF into In/Ni-MOF through exchanging the Ni2+ ion with In3+ ion can prevent the destruction of the porous reticular skeleton and hierarchical structure of Ni-MOF during calcination. Thus, the mesoporous In2O3-NiO hollow composites possess high porosity and large specific surface area (55.5 m2 g-1), which can produce sufficient permeability pathways for volatile organic compound (VOCs) molecules, maximize the active sites, and enhance the capacity of VOC capture. The mesoporous In2O3-NiO-based sensors exhibit enhanced triethylamine (TEA) sensing performance (S = 33.9-100 ppm) with distinct selectivity, good long-term stability, and lower detection limit (500 ppb) at 200 °C. These results can be attributed to the mesoporous hollow hierarchical structure and p-n junction of In2O3-NiO. The preparation concept mentioned in this work may provide a versatile platform applicable to various mesoporous composite sensing material-based hollow structures.

Hierarchical Assembly of α-Fe2O3 Nanorods on Multiwall Carbon Nanotubes as a High-Performance Sensing Material for Gas Sensors.

This paper presents a facile hydrolysis reaction and annealing for preparing a novel hierarchical nanoheterostructure via assembly of α-Fe2O3 nanorods onto multiwall carbon nanotubes (MWCNTs) backbones. The as-synthesized nanocomposites were characterized using XRD (X-ray diffraction), FESEM (Field emission scanning electron microscopy), TEM (Transmission electron microscopy), XPS (X-ray photoelectron spectroscopy) and BET (Surface Area and Porosity System). The observations showed uniform α-Fe2O3 nanorods approximately 100-200 nm in length and 50-100 nm in diameter that were hierarchically assembled onto the surface of the MWCNTs. The formation of the heterostructure was investigated by observing the evolution of the microstructure of the products at different reaction times. The X-ray photoelectron spectra (XPS) showed that the ability of the absorbing oxygen was enhanced by the formation of the heterostructure composites. Moreover, as a proof-of-concept presentation, the novel CNTs@α-Fe2O3 hierarchical heterostructure acted as a gas sensitive material. Significantly, the composites exhibited excellent sensing properties for acetone with high sensitivity, exceptional selectivity and good reproducibility. The response of the CNTs@α-Fe2O3 sensor to 100 ppm acetones at 225 °C was nearly 35, which was superior to the single α-Fe2O3 nanorods with a response of 16, and the detection limit of the sensor was 500 ppb. The enhanced properties were mainly attributed to the unique structure and p-n heterojunction between the CNTs and the α-Fe2O3 nanorods.

Acetone gas sensor based on NiO/ZnO hollow spheres: Fast response and recovery, and low (ppb) detection limit.

NiO/ZnO composites were synthesized by decorating numerous NiO nanoparticles on the surfaces of well dispersed ZnO hollow spheres using a facile solvothermal method. Various kinds of characterization methods were utilized to investigate the structures and morphologies of the hybrid materials. The results revealed that the NiO nanoparticles with a size of ∼10nm were successfully distributed on the surfaces of ZnO hollow spheres in a discrete manner. As expected, the NiO/ZnO composites demonstrated dramatic improvements in sensing performances compared with pure ZnO hollow spheres. For example, the response of NiO/ZnO composites to 100ppm acetone was ∼29.8, which was nearly 4.6 times higher than that of primary ZnO at 275°C, and the response/recovery time were 1/20s, respectively. Meanwhile, the detection limit could extend down to ppb level. The likely reason for the improved gas sensing properties was also proposed.

Self-assembled chiral helical nanofibers by amphiphilic dipeptide derived from d- or l-threonine and application as a template for the synthesis of Au and Ag nanoparticles.

The discovery of a class of self-assembling peptides that spontaneously undergo self-organization into well-ordered structures opened a new avenue for molecular fabrication of biological materials. In this paper, the structure controlled helical nanofibers were prepared by two artificial ß-sheet dipeptides with long alkyl chains derived from l- and d-threonine (Thr) and sodium hydroxide (NaOH). These helical nanofibers have been characterized using transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), circular dichroism (CD), Fourier transform infrared (FT-IR) spectroscopy, and X-ray powder diffraction (XRD). It was demonstrated that the helicity of the nanofibers could be easily controlled by changing the chirality of the constituent amino acids in the peptide species (d- or l-threonine). Moreover, the hydrogen bonding interactions between the amide groups as well as the hydrophobic interactions among the alkyl chains play important roles in the self-assembly process. It also can be observed that with the passage of time, the hydrogen bonding interactions between the individual nanofiber induced the conversion from nanofibers to nanobelts. Particularly, gold and silver nanoparticles performed good catalytic ability were synthesized using the assembled nanofibers as template.