CarbonIron Electron Transport Channels in Porphyrin-Graphene Complex for ppb-Level Room Temperature NO Gas Sensing.

It is a great challenge to develop efficient room-temperature sensing materials and sensors for nitric oxide (NO) gas, which is a biomarker molecule used in the monitoring of inflammatory respiratory diseases. Herein, Hemin (Fe (III)-protoporphyrin IX) is introduced into the nitrogen-doped reduced graphene oxide (N-rGO) to obtain a novel sensing material HNG-ethanol. Detailed XPS spectra and DFT calculations confirm the formation of carbon-iron bonds in HNG-ethanol during synthesis process, which act as electron transport channels from graphene to Hemin. Owing to this unique chemical structure, HNG-ethanol exhibits superior gas sensing properties toward NO gas (Ra /Rg  = 3.05, 20 ppm) with a practical limit of detection (LOD) of 500 ppb and reliable repeatability (over 5 cycles). The HNG-ethanol sensor also possesses high selectivity against other exhaled gases, high humidity resistance, and stability (less than 3% decrease over 30 days). In addition, a deep understanding of the gas sensing mechanisms is proposed for the first time in this work, which is instructive to the community for fabricating sensing materials based on graphene-iron derivatives in the future.

Synergy of CO2-response and aggregation induced emission in a small molecule: renewable liquid and solid CO2 chemosensors with high sensitivity and visibility.

A tetraphenylethylene (TPE) derivative (N,N-dimethyl-N'-(4-(1,2,2-triphenylvinyl)phenyl)acetimidamide, TPE-amidine) was designed and synthesized, and used to prepare visible CO2 chemosensors, TPE-amidine-L (liquid) and TPE-amidine-S (solid). The hydrophilicity of TPE-amidine thoroughly changed because of the unique reversible reaction between the amidine group and CO2, which controlled the molecular aggregation extent in water by CO2. Combining with the well-known aggregate-induced emission effect, the highly selective CO2 chemosensor TPE-amidine-L was developed, which has the lowest CO2 detection limit of 24.6 ppm compared with other reported CO2 chemosensors, and can be regenerated within 10 s by adding triethylamine. With the aim of being safer and more convenient to use, a polyacrylamide hydrogel containing TPE-amidine was prepared as a renewable CO2 sensing "tape" (TPE-amidine-S). The flexibility, adhesivity, CO2 sensitivity and reversibility of the "tape" is systematically investigated, showing great potential for "on-site" and "real-time" CO2 detection in practical applications.

A simple functionalized silica microsphere for fast PETN vapor detection based on fluorescence color changes via a catalyzed oxidation process.

In this work, we report a new fluorescent material for pentaerythritol tetranitrate (PETN) vapor detection. A series of fluorene substituted vinyl-SiO microspheres with different ratios has been designed and easily synthesized. Sensing films on quartz plates were obtained by a solid phase transfer method. With a specific diameter of SiO and a specific density of surrounding fluorene, the microspheres performed a rapid fluorescence color change via oxidation with highly selective PETN catalysis. The emission peak at 355 nm was rapidly quenched while an enhancement at 525 nm appeared under exposure to PETN saturated vapor. Herein, we present this fluorescent silica nanoparticle as an excellent sensing material towards vapor phase PETN, making contributions to many fields such as public security and military use.

Concise and Efficient Fluorescent Probe via an Intromolecular Charge Transfer for the Chemical Warfare Agent Mimic Diethylchlorophosphate Vapor Detection.

Sarin, used as chemical warfare agents (CWAs) for terrorist attacks, can induce a number of virulent effects. Therefore, countermeasures which could realize robust and convenient detection of sarin are in exigent need. A concise charge-transfer colorimetric and fluorescent probe (4-(6-(tert-butyl)pyridine-2-yl)-N,N-diphenylaniline, TBPY-TPA) that could be capable of real-time and on-site monitoring of DCP vapor was reported in this contribution. Upon contact with DCP, the emission band red-shifted from 410 to 522 nm upon exposure to DCP vapor. And the quenching rate of TBPY-TPA reached up to 98% within 25 s. Chemical substances such as acetic acid (HAc), dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PAMP), and triethyl phosphate (TEP) do not interfere with the detection. A detection limit for DCP down to 2.6 ppb level is remarkably achieved which is below the Immediately Dangerous to Life or Health concentration. NMR data suggested that a transformation of the pyridine group into pyridinium salt via a cascade reaction is responsible for the sensing process which induced the dramatic fluorescent red shift. All of these data suggest TBPY-TPA is a promising fluorescent sensor for a rapid, simple, and low-cost method for DCP detection, which could be easy to prepare as a portable chemosensor kit for its practical application in real-time and on-site monitoring.

Si, O-Codoped Carbonized Polymer Dots with High Chemiresistive Gas Sensing Performance at Room Temperature.

A new type of carbonized polymer dot was prepared by the one-step hydrothermal method of triethoxylsilane (TEOS) and citric acid (CA). The sensor made from carbonized polymer dots (CPDs) showed superior gas sensing performance toward ammonia at room temperature. The Si, O-codoped CPDs exhibited superior ammonia sensing performance at room temperature, including a low practical limit of detection (pLOD) of 1 ppm (Ra/Rg: 1.10, 1 ppm), short response/recovery time (30/36 s, 1 ppm), high humidity resistance (less than 5% undulation when changing relative humidity to 80 from 30%), high stability (less than 5% initial response undulation after 120 days), reliable repeatability, and high selectivity against other interferential gases. The gas sensing mechanism was investigated through control experiments and in situ FTIR, indicating that Si, O-codoping essentially improves the electron transfer capability of CPDs and synergistically dominates the superior ammonia sensing properties of the CPDs. This work presents a facile strategy for constructing novel high-performance, single-component carbonized polymer dots for gas sensing.

Carbon Dots Embedded in Cellulose Film: Programmable, Performance-Tunable, and Large-Scale Subtle Fluorescent Patterning by in Situ Laser Writing.

Fluorescent patterns with multiple functions enable high-security anti-counterfeiting labels. Complex material synthesis and patterning processes limit the application of multifunctional fluorescent patterns, so the technology of in situ fluorescent patterning with tunable multimodal capabilities is becoming more necessary. In this work, an in situ fluorescent patterning technology was developed using laser direct writing on solid cellulose film at ambient conditions without masks. The fluorescent intensity and surface microstructure of the patterns could be adjusted by programmable varying of the laser parameters simultaneously. During laser direct writing, carbon dots are generated in situ in a cellulose ester polymer matrix, which significantly simplifies the fluorescent patterning process and reduces the manufacturing cost. Interestingly, the tunable fluorescent intensity empowers the fabrication of visual stereoscopic fluorescent patterns with excitation dependence, further improving its anti-counterfeiting performance. The obtained fluorescent patterns still show ultrahigh optical properties after being immersed in an acid/base solution (pH 5-12) over one month. In addition, the anti-UV performance of the obtained laser-patterned film with transmittance around 90% is comparable to that of commercial UV-resistant films. This work provided an advanced and feasible approach to fabricating programmable, performance-tunable, subtle fluorescent patterns in large-scale for industrial application.

Assembly of Core/Shell Nanospheres of Amorphous Hemin/Acetone-Derived Carbonized Polymer with Graphene Nanosheets for Room-Temperature NO Sensing.

Implementing parts per billion-level nitric oxide (NO) sensing at room temperature (RT) is still in extreme demand for monitoring inflammatory respiratory diseases. Herein, we have prepared a kind of core-shell structural Hemin-based nanospheres (Abbr.: Hemin-nanospheres, defined as HNSs) with the core of amorphous Hemin and the shell of acetone-derived carbonized polymer, whose core-shell structure was verified by XPS with argon-ion etching. Then, the HNS-assembled reduced graphene oxide composite (defined as HNS-rGO) was prepared for RT NO sensing. The acetone-derived carbonized polymer shell not only assists the formation of amorphous Hemin core by disrupting their crystallization to release more Fe-N4 active sites, but provides protection to the core. Owing to the unique core-shell structure, the obtained HNS-rGO based sensor exhibited superior RT gas sensing properties toward NO, including a relatively higher response (Ra/Rg = 5.8, 20 ppm), a lower practical limit of detection (100 ppb), relatively reliable repeatability (over 6 cycles), excellent selectivity, and much higher long-term stability (less than a 5% decrease over 120 days). The sensing mechanism has also been proposed based on charge transfer theory. The superior gas sensing properties of HNS-rGO are ascribed to the more Fe-N4 active sites available under the amorphous state of the Hemin core and to the physical protection by the shell of acetone-derived carbonized polymer. This work presents a facile strategy of constructing a high-performance carbon-based core-shell nanostructure for gas sensing.

Charge transfer driven by redox dye molecules on graphene nanosheets for room-temperature gas sensing.

Special functional groups to modify the surface of graphene have received much attention since they enable the charge transfer enhancement, thus realizing gas-sensing at room temperature. In this work, three typical redox dye molecules, methylene blue (MB), indigo carmine (IC) and anthraquinone-2-sulfonate (AQS), were selected to be supramolecularly assembled with reduced graphene oxide (rGO), respectively. Remarkably, three graphene-based materials AQS-rGO (response = 3.2, response time = 400 s), IC-rGO (response = 4.3, response time = 300 s) and MB-rGO (response = 7.1, response time = 100 s) exhibited excellent sensitivity and short response time toward 10 ppm NO2 at room temperature. The corresponding NO2 sensing mechanism of the obtained materials was further investigated by cyclic voltammetry (CV) measurements. CV was conducted to measure the anodic peak potential (Epa) of three redox dyes. Interestingly, it is obvious that the Epa values were positively correlated with the gas sensitivity and response time of the three materials. To explore the mechanism, UV-vis spectroscopy was adopted to analyze the lowest unoccupied molecular orbitals (LUMOs) of three redox dye molecules. The results show that the oxidation abilities of three redox dyes were also positively correlated with the gas sensitivity and response time of three corresponding graphene-based materials.

A simple but highly efficient multi-formyl phenol-amine system for fluorescence detection of peroxide explosive vapour.

A simple, highly stable, sensitive and selective fluorescent system for peroxide explosives was developed via an aromatic aldehyde oxidation reaction. The high efficiency arises from its higher HOMO level and multiple H-bonding. The sensitivity is obtained to be 0.1 ppt for H2O2 and 0.2 ppb for TATP.

Femtogram level detection of nitrate ester explosives via an 8-pyrenyl-substituted fluorene dimer bridged by a 1,6-hexanyl unit.

Compared with nitroaromatic explosives detection, nitrate esters are far from wide attention possibly because of their shortage of aromatic ring and difficulty in being detected. Three fluorescent chemical probes for trace nitrate ester detection: an intramolecular dimer (P3) of 8-pyrenyl-substituted fluorenes bridged by a 1,6-hexanyl unit as well as its counterparts 2PR-F (P1) and 2PR-Cz (P2) has been synthesized and characterized. Their chemical structures and photophysical and electrochemical properties show that the dimer P3 film has a higher molar extinction coefficient, larger steric hindrance, higher area-to-volume ratio, and matching energy level with nitrate ester explosives, which contributes to higher sensitivity and moderate selectivity for sensing of nitrate ester explosives such as nitroglycerin (NG). The fluorescence of the P3 film is rapidly about 90% quenched upon exposure to a saturated vapor of NG for 50 s and almost 100% quenched for 300 s at room temperature due to photoinduced electron transfer between the probe and analyte. In addition, a very sensitive, rapid, simple, and low-cost surface-sensing method by disposable filter-paper-based test strips is demonstrated. The contact-mode approach exhibits a detection limit as low as 0.5 fg/cm(2) for NG. These results reveal that the multiple-pyrenyl-unit-substituted fluorene dimer P3 is suitable for preparing a highly sensitive and efficient thin-film device for detecting nitrate esters.

A mild and catalyst-free conversion of solid phase benzylidenemalononitrile/benzylidenemalonate to N-benzylidene-amine and its application for fluorescence detection of primary alkyl amine vapor.

A new rapid and catalyst-free solid/vapor reaction between benzylidenemalonate/benzylidenemalononitrile and primary alkyl amines was found. With these as sensory units of fluorescent polymers, probes for primary amine vapor with high sensitivity and selectivity were developed.

A BODIPY dye as a reactive chromophoric/fluorogenic probe for selective and quick detection of vapors of secondary amines.

A new reaction based fluorescence turn-off strategy for detection of secondary amines was developed. The probe shows fast response and high selectivity to secondary amines in solution/film at sub-ppm levels through chromogenic and fluorescent dual-mode signal changes.