A new strategy for RRS-based determination of phosphate with a bifunctional Fe3O4 magnetic nanoparticle surface molecularly imprinted polydopamine probe.

In this paper, a magnetic nanoparticle surface molecularly imprinted polydopamine RRS probe Fe3O4@MIP was prepared using phosphomolybdic acid (PMo) as the template, Fe3O4 magnetic nanoparticles as the substrate and dopamine hydrochloride (PD) as the monomer and crosslinking agent for the determination of PO43-. Under acidic conditions, phosphomolybdic acid is formed by the reaction of PO43- with ammonium molybdate (MSA), which can be imprinted with the Fe3O4@MIP probe surface and reduced to phosphomolybdic blue (PMoB) by ascorbic acid (Aa). Strong resonance Rayleigh scattering energy transfer (RRS-ET) occurs between the probe and PMoB, resulting in a decrease in the RRS signal value. A new, simple and selective RRS method for the determination of PO43- in water samples was developed. The linear range of this method is 1-22.5 µmol L-1, and the detection limit (DL) is 0.49 µmol L-1. Furthermore, the magnetic enrichment ability of Fe3O4@MIP is discussed. Experimental data show that even 0.2 µmol L-1 of phosphate can be detected within a 20% error range.

A new surface molecularly imprinted polyacrylamide nanoprobe for trace Cr(VI) with RRS technique.

This article was used potassium dichromate as the template molecule, silver nanoclusters as the nano matrix, acrylamide as the monomer, ethylene glycol dimethacrylate (EGDMA) as the crosslinking agent, and azodiisobutyronitrile (AIBN) as the initiator to prepare a new silver nanocluster surface MIP (AgNCs@MIP) nanoprobe for chromate. Upon addition of Cr(VI), it selectively adsorbs on the surface of AgNCs@MIP nanoprobes. The dichromate ion absorption peak at 350 nm overlaps with the AgNCs@MIP RRS peak at 370 nm, resulting in strong RRS energy transfer (RRS-ET) and a decrease in the RRS intensity. The decreased RRS intensity is directly proportional to the concentration of dichromate ions in the range of 0.0025-0.015 µmol/L, with a detection limit of 0.8 nmol/L. Therefore, a simple, fast, sensitive and selective RRS method for the determination of trace Cr(VI) in mineral water has been established, with a relative standard deviation of 9.2-9.8 % and recovery of 95.20 %-103.60 %.

Rapid and selective RRS determination of ferrocyanide with a nanogold surface molecularly imprinted polymethacrylic acid probe.

In this work, a nanogold surface molecularly imprinted polymer spectral probe (AuNP@MIP) for selectively identifying ferrocyanide was prepared under microwave irradiation using nanogold as the core, ferrocyanide as the template ion, methacrylic acid as the monomer, and ethylene glycol dimethacrylate as the cross-linking agent. AuNP@MIP was found to produce a resonance Rayleigh scattering (RRS) peak at 370 nm. When potassium ferrocyanide (K4Fe(CN)6) was present, a AuNP@MIP-Fe(CN)6 complex was formed, producing RRS-energy transfer (RRS-ET). With an increase in ferrocyanide concentration within a certain range, the RRS intensity at 370 nm decreased linearly, and the detection range was 0.02-0.40 µmol L-1, with a detection limit as low as 0.006 µmol L-1 ferrocyanide. This new method has the advantages of simplicity, rapidity, and selectivity when applied for the determination of K4Fe(CN)6 in table salt.

A new copper nanocluster surface molecular imprinted polymethacrylic acid probe for ultratrace trichlorophenol based on in situ-generated nanogold SPR effects.

A new coinage metal nanocluster surface molecularly imprinted polymethacrylic acid nanoprobe (NC@MIP) for the selective determination of 2,4,6-trichlorophenol (TCP) was prepared via microwave synthesis using 2,4,6-trichlorophenol as a template molecule, copper nanoclusters (CuNC) as a nanosubstrate, and methacrylic acid as a polymer monomer. It was found that the copper nanocluster MIP (CuNC@MIP) shows the strongest catalytic performance for the reduction of HAuCl4 by hydrazine hydrate for the on-site generation of gold nanoparticles (AuNPs) with the surface plasmon resonance (SPR) effects of resonance surface-enhanced Raman scattering (SERS) and resonance Rayleigh scattering (RRS) as well as absorption (Abs). When TCP was added, the CuNC@MIP nanoprobe and TCP-formed CuNC@MIP-TCP nanoenzyme with stronger catalytic activity generated more AuNPs, and the trimodal analytical signal was enhanced linearly. Therefore, a new SERS/RRS/Abs trimodal sensing platform for TCP was constructed, which was simple, rapid, sensitive, and selective. For each mode, the linear ranges were 0.0075-0.075, 0.010-0.10, and 0.010-0.10 nmol L-1, and the detection limits were 0.0010, 0.021, and 0.043 nmol L-1, respectively. The relative deviation of TCP in different water quality was 0.47%-2.5% and the recovery rate was 94.6%-108.6%.

Dual-Strategy Tailoring Molecular Structures of Dopant-Free Hole Transport Materials for Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transport materials (HTMs) are ideal materials for highly efficient and stable n-i-p perovskite solar cells (PSCs), but most current design strategies for tailoring the molecular structures of HTMs are limited to single strategy. Herein, four HTMs based on dithienothiophenepyrrole (DTTP) core are devised through dual-strategy methods combining conjugate engineering and side chain engineering. DTTP-ThSO with ester alkyl chain that can form six-membered ring by the S⋅⋅⋅O noncovalent conformation lock with thiophene in the backbone shows good planarity, high-quality film, matching energy level and high hole mobility, as well as strong defect passivation ability. Consequently, a remarkable power conversion efficiency (PCE) of 23.3 % with a nice long-term stability is achieved by dopant-free DTTP-ThSO-based PSCs, representing one of the highest values for un-doped organic HTMs based PSCs. Especially, the fill factor (FF) of 82.3 % is the highest value for dopant-free small molecular HTMs-based n-i-p PSCs to date. Moreover, DTTP-ThSO-based devices have achieved an excellent PCE of 20.9 % in large-area (1.01 cm2) devices. This work clearly elucidates the structure-performance relationships of HTMs and offers a practical dual-strategy approach to designing dopant-free HTMs for high-performance PSCs.

A Dimode Scattering Method for Ultratrace Dinitrofuran Detection with Nanopalladium Molecularly Imprinted Polymer Nanocatalytic Probe.

With four nanoparticles as the nanomatrix, dinotefuran (DNF) as the template molecule, N-isopropylacrylamide as the functional monomer, trimethylolpropane and trimethacrylate as the cross-linker, four nanosurface molecularly imprinted polymer (MIP) bifunctional probes were prepared by microwave synthesis. It was found that palladium nanosurface MIP (Pd@MIP) not only recognized DNF but also had the strongest catalytic effect on the new nanogold indicator reaction of acrylic acid-HAuCl4, which was evaluated quickly with the slope procedure developed by us. The generated gold nanoparticles (AuNPs) not only possessed the resonance Rayleigh scattering (RRS) effect but also strong surface-enhanced Raman scattering (SERS) activity. The combination of Pd@MIP with DNF enhanced the catalytic effect by coupling the nanosurface electrons with π-electrons, thus enhancing both scattering signals. A new Pd@MIP nanoprobe catalytic-SERS/RRS dual-mode analytical platform was developed for the specific and sensitive detection of DNF. The linear ranges of the SERS and RRS methods were 0.075-0.75 and 0.1-0.75 nmol/L, and the limits of detection were 0.03 and 0.06 nmol/L, respectively. The standard deviations were 0.54-2.39%, and the recoveries were 93-105%.

Tunneling-Driven Marcus-Inverted Triplet Energy Transfer in a Two-Dimensional Perovskite.

Quantum tunneling, a phenomenon that allows particles to pass through potential barriers, can play a critical role in energy transfer processes. Here, we demonstrate that the proper design of organic-inorganic interfaces in two-dimensional (2D) hybrid perovskites allows for efficient triplet energy transfer (TET), where quantum tunneling of the excitons is the key driving force. By employing temperature-dependent and time-resolved photoluminescence and pump-probe spectroscopy techniques, we establish that triplet excitons can transfer from the inorganic lead-iodide sublattices to the pyrene ligands with rapid and weakly temperature-dependent characteristic times of approximately 50 ps. The energy transfer rates obtained based on the Marcus theory and first-principles calculations show good agreement with the experiments, indicating that the efficient tunneling of triplet excitons within the Marcus-inverted regime is facilitated by high-frequency molecular vibrations. These findings offer valuable insights into how one can effectively manipulate the energy landscape in 2D hybrid perovskites for energy transfer and the creation of diverse excitonic states.

A new N/Fe doped carbon dot nanosurface molecularly imprinted polymethacrylate nanoprobe for trace fipronil with SERS/RRS dimode technique.

The N and Fe doped carbon dot (CDNFe) was prepared by microwave procedure. Using CDNFe as the nano-substrate, fipronil (FL) as the template molecule and α-methacrylic acid as the functional monomer, the molecular imprinted polymethacrylic acid nanoprobe (CDNFe@MIP) with difunction was synthesized by microwave procedure. The CDNFe@MIP was characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier infrared spectroscopy, and other techniques. The results show that the nanoprobe not only distinguish FL but also has a strong catalytic effect on the HAuCl4-Na2C2O4 nanogold indicator reaction. When the nanoprobes specifically recognize FL, their catalytic effect is significantly reduced. Since the AuNPs generated by HAuCl4 reduction have strong surface-enhanced Raman scattering (SERS) and resonance Rayleigh scattering (RRS) effects, a SERS/RRS dual-mode sensing platform for detecting 5-500 ng/L FL was constructed. The new analytical method was applied to detect FL in food samples with a relative standard deviation (RSD) of 3.3-8.1 % and a recovery rate of 94.6-104.5 %.

A novel bifunctional molecularly imprinted polymer-based SERS/RRS dimode nanosensor for ultratrace acetamiprid.

A new acetamiprid (AP) molecularly imprinted polymer (MIP) nanosol was synthesized with α-methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker and 2,2'-azobisisobutyronitrile as initiator, under the microwave irradiation. It was characterized by transmission electron microscopy, specific surface area and pore size analysis, and molecular spectroscopy. The bifunctional MIP nanomaterial not only had the recognition of AP but also had a strong catalysis of the nanogold dimode indicator reaction of chloroauric acid-dopamine. The generated gold nanoparticles (AuNPs) had strong surface-enhanced Raman scattering (SERS) and resonance Rayleigh scattering (RRS) effects, and the two kinds of signals enhanced linearly with imprinted molecule AP increasing. Accordingly, a novel SERS/RRS nanosensor platform was constructed to detect 0.25-20 pmol/L and 0.5-50 pmol/L AP by SERS and RRS monitoring respectively. Moreover, a reliable nanocatalytic mechanism was proposed.

Nanogold sol plasmon discattering assay for trace carbendazim in tea coupled aptamer with Au3+-glyoxal-carbon dot nanocatalytic reaction.

Carbendazim (CBZ) is a broad-spectrum fungicide, which is toxic to mammals. Therefore, it is very necessary to establish a sensitive detection for food safety. An experiment found that CDFe exhibited excellent catalysis for the nano-indicator reaction of HAuCl4-glyoxal to produce gold nanoparticles (AuNPs) and that the generated AuNPs have a very strong surface-enhanced Raman scattering (SERS) effect at 1613 cm-1 in the presence of Victoria blue B molecular probes, and resonance Rayleigh scattering (RRS) signals at 370 nm. The aptamer (Apt) suppressed the catalysis of CDFe to cause the SERS and RRS signals decreasing. With the addition of CBZ, the specific Apt reaction occurred to restore the catalysis of CDFe, and resulting in a linear increase in the signals of RRS and SERS. As a result, this new nanocatalytic amplification indicator reaction was coupled with a specific Apt reaction of carbendazim (CBZ), to construct a new CDFe catalytic amplification-aptamer SERS/RRS discattering assay for ultratrace CBZ, which was used to analyze CBZ in tea samples with satisfactory results. In addition, this biosensoring platform can be also used to assay profenofos.

Novel Pyrimidine-Based Iridium Complexes with Bulky Charge-Carrier Groups as Dopants for Highly Efficient Green Polymer Light-Emitting Diodes.

Two new pyrimidine-based iridium complexes with triphenylamine and tetraphenylsilane, namely (TPAPr)2 IrAcac and (TPSPr)2 IrAcac, were fully synthesized and characterized. Both of the targeted iridium complexes exhibit excellent thermal stability and high photoluminescence quantum yields. Compared to (TPAPr)2 IrAcac, (TPSPr)2 IrAcac achieved its highest PLQY and current efficiency (CE) at higher dopant concentration probably because of its bulky tetraphenylsilane group, which can effectively suppress the concentration quenching. However, according to DFT studies, (TPSPr)2 IrAcac shows faster non-radiative transitions due to the presence of more excited-state distortions than (TPAPr)2 IrAcac. As a result, Green phosphorescent polymer light-emitting diodes (PLEDs) containing (TPAPr)2 IrAcac and (TPSPr)2 IrAcac as dopants exhibit exceptional device performance with peak CE values of 38.24 and 36.06 cd A-1 , respectively. (TPAPr)2 IrAcac exhibited a superior efficiency than (TPSPr)2 IrAcac because of its high Φp , low RMSD value, and efficient energy transfer from the host to the guest. More importantly, the PLEDs based on (TPAPr)2 IrAcac and (TPSPr)2 IrAcac show stable phosphorescent emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.313, 0.497) and (0.299, 0.483), respectively. This work points out a viable method for creating phosphorescent iridium complexes based on pyrimidine for high-efficiency organic light-emitting diodes (OLEDs).

Liquid Crystal@Nanosilver Catalytic Amplification-Aptamer Trimode Biosensor for Trace Pb2.

Liquid crystals (LCs) are a very important display material. However, the use of LC, especially LC-loaded nanoparticles, as a catalyst to amplify the analytical signal and coupled with specific aptamer (Apt) as a recognition element to construct a highly sensitive and selective three-mode molecular spectral assay is rarely reported. In this article, five LCs, such as cholesteryl benzoate (CB), were studied by molecular spectroscopy to indicate the liquid crystal nanoparticles in the system, and highly catalytic and stable CB loaded-nanosilver (CB@AgNPs) sol was prepared. The slope procedure was used to study the catalysis of the five LCs and CB@AgNPs on the new indicator reaction between AgNO3 and sodium formate (Fo) to produce silver nanoparticles (AgNPs) with a strong surface plasmon resonance absorption (Abs) peak at 450 nm, a resonance Rayleigh scattering (RRS) peak at 370 nm and a surface enhanced Raman scattering (SERS) peak at 1618 cm-1 in the presence of molecular probes. By coupling the new CB@AgNPs catalytic indicator reaction with the Apt reaction, a new CB@AgNPs catalytic amplification-SERS/RRS/Abs trimode biosensoring platform was constructed for detecting inorganic pollutants, such as Pb2+, Cd2+, Hg2+ and As3+.

MXene nanosheet loaded gold nanocluster catalytic amplification-aptamer SERS quantitative assay platform for isocarbophos.

The traditional preparation of MXeneTi3C2 is complicated. Two-dimensional MXeneTi3C2 nanosheets were prepared via in-situ generation of HF etching Ti3AlC2 under the microwave irradiation. Gold nanocluster doped nanosheets sol (MXene@Au) with excellent stability and strong catalysis was synthesized with no product residue reducer CO. MXene@Au nanosol can catalyze mandelic acid-HAuCl4 to produce gold nanoparticles, which can be traced via resonance Rayleigh scattering (RRS) and surface-enhanced Raman scattering (SERS). Coupled the dual-mode nanocatalytic indicator reaction with aptamer reaction, a high sensitivity, selectivity, facile SERS/RRS dual-mode biosensnoring assay platform has been constructed for isocarbophos (ICP). The linear range of SERS was 1.0 × 10-3-2.5 × 10-2 nmol/L, with a detection of limit 4.5 × 10-5 nmol/L (S/N = 3). It has been used to detect ICP in water samples, with a good recovery (95.5-104%) and a good relative standard deviation (5.2-9.6%). This new nanocatalytic amplification biosensoring strategy can also assay other organic pesticides including malathion, glyphosate, profenofos and carbendazim. In addition, the nanocatalytic mechanism was investigated.

Aptamer Trimode Biosensor for Trace Glyphosate Based on FeMOF Catalytic Oxidation of Tetramethylbenzidine.

The stable and highly catalytic Fe metal-organic framework (FeMOF) nanosol was prepared and characterized by electron microscopy, and energy and molecular spectral analysis. It was found that FeMOF strongly catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to produce TMBox, which had a fluorescence (FL) peak at 410 nm. When silver nanoparticles were added, it exhibited strong resonance Rayleigh scattering (RRS) activity and surface-enhanced Raman scattering (SERS) effect. This new FeMOF nanocatalytic trimode indicator reaction was combined with the glyphosate aptamer reaction to establish a new SERS/RRS/FL trimode biosensor for glyphosate. The sensor can be used for the analysis of environmental wastewater, and a new method for detecting glyphosate content in wastewater is proposed. The linear range of the sensor is 0.1-14 nmol/L, the detection limit is 0.05 nmol/L, the recovery is 92.1-97.5%, and the relative standard deviation is 3.6-8.7%.

Ti3C2@Pd nanocatalytic amplification-polypeptide SERS/RRS/Abs trimode biosensoring platformfor ultratrace trinitrotoluene.

A new MXene supported Pd nanoparticles (Ti3C2@Pd) nanosol with good stability and strong catalysis was prepared by the two-step procedure. Experiment was found that Ti3C2@Pd could strongly catalyze the reduction of HAuCl4 by H2O2 to produce gold nanoparticles (AuNPs), with strong surface enhanced Raman scattering (SERS), resonance Rayleigh scattering (RRS) and surface plasmon resonance absorption (Abs). Coupled this new SERS/RRS/Abs trimode nanocatalytic indicator reaction with specific TNT polypeptide (PTTNT), a facile and selective trimode polypeptide biosensoring platform was established for the detection of ultratrace TNT, with a linear range of 1.1-66, 1.1-66 and 4.4-66 pmol/L TNT, and detection limit (DL) of 0.69, 0.97 and 3.36 pmol/L by SERS, RRS and Abs assay respectively. It has been used to detect TNT in wastewater and soil samples, with recovery of 98.7-106% and RSD of 6.22-8.77%. In addition, this biosensoring platform can be also used to assay glyphosate and estradiol, respectively.

A facile COF loaded-molybdate resonance Rayleigh scattering and fluorescence dimode probe for determination of trace PO43.

A new covalent organic framework loaded-molybdate (COFMo) nanomaterial was prepared simply by solvothermal procedure and characterized by electron microscopy and molecular spectral techniques. The COFMo had a strong resonance Rayleigh scattering (RRS) signal at 465 nm and a fluorescence peak at 345 nm. When the PO43- was added in the system, it reacted with the molybdate, which loaded on the surface of COF particles, to form stable phosphomolybdic acid occurring RRS/fluorescence-energy transfer, the RRS and fluorescence signals were decreased. The decreased RRS/fluorescence intensities were linear to the PO43- concentration in the range of 0.053-3.2 nmol/L and 0.10-3.2 nmol/L, with a detection limit of 0.050 nmol/L and 0.090 nmol/L respectively. Accordingly, a new and facile RRS/fluorescence dimode method for detection of trace PO43- was established, only one fluorometer was used.

Highly catalysis amplification of MOFNd-loaded nanogold combined with specific aptamer SERS/RRS assay of trace glyphosate.

A neodymium metal-organic framework (MOFNd) was prepared using 1H-pyrazole-3,5-dicarboxylic acid (H3pdc) and 2-pyrazinecarboxylic acid as ligands. Through the addition of HAuCl4 as a precursor and NaBH4 as a reducing agent, a new MOFNd-loaded nanogold (AuNPs) (Au@MOFNd) nanosol with good stability and high catalytic activity was conveniently prepared via a solvothermal-reduction method and characterized. It was found that the indicator reaction of reducing HAuCl4 by Na2SO3 to generate AuNPs was slow. Au@MOFNd strongly catalyzes this nanoreaction, and the produced AuNPs exhibit a strong resonance Rayleigh scattering (RRS) peak at 370 nm, and a strong surface-enhanced Raman scattering (SERS) peak at 1617 cm-1 with the addition of the molecular probe Victoria blue 4R (VB4r). A novel SERS/RRS di-mode quantitative analysis method for glyphosate (GLY) was established by coupling this new Au@MOFNd catalytic indicator reaction with the aptamer (Apt) reaction of GLY, with SERS and RRS detection limits of 0.02 nM and 0.3 nM, respectively. It has been applied to the analysis of soil samples with a recovery rate of 93.0%-106.5% and precision of 2.2%-4.1%, and the results were satisfactory.

Aptamer-Adjusted Carbon Dot Catalysis-Silver Nanosol SERS Spectrometry for Bisphenol A Detection.

Carbon dots (CDs) can be prepared from various organic (abundant) compounds that are rich in surfaces with -OH, -COOH, and -NH2 groups. Therefore, CDs exhibit good biocompatibility and electron transfer ability, allowing flexible surface modification and accelerated electron transfer during catalysis. Herein, CDs were prepared using a hydrothermal method with fructose, saccharose, and citric acid as C sources and urea as an N dopant. The as-prepared CDs were used to catalyze AgNO3-trisodium citrate (TSC) to produce Ag nanoparticles (AgNPs). The surface-enhanced Raman scattering (SERS) intensity increased with the increasing CDs concentration with Victoria blue B (VBB) as a signal molecule. The CDs exhibited a strong catalytic activity, with the highest activity shown by fructose-based CDs. After N doping, catalytic performance improved; with the passivation of a wrapped aptamer, the electron transfer was effectively disrupted (retarded). This resulted in the inhibition of the reaction and a decrease in the SERS intensity. When bisphenol A (BPA) was added, it specifically bound to the aptamer and CDs were released, recovering catalytical activity. The SERS intensity increased with BPA over the concentration range of 0.33-66.67 nmol/L. Thus, the aptamer-adjusted nanocatalytic SERS method can be applied for BPA detection.

Highly catalysis MOFCe supported Ag nanoclusters coupled with specific aptamer for SERS quantitative assay of trace dopamine.

A cerium metal organic framework-loaded silver nanocluster (MOFCeAgNC) is synthesized by a facile stirring procedure with trimesic acid, cerium nitrate, silver nitrate and NaBH4, which exhibites strong catalytic activity in the indicated reaction of HAuCl4-sodium lactate (SL). MOFCeAgNC can sensitively detect dopamine (DA) by surface-enhanced Raman scattering (SERS) and resonance Rayleigh scattering (RRS) techniques with a detection concentration range of 0.01-0.25 nmol/L and a detection limit of 0.008 nmol/L. Based on the specific binding of aptamer (Apt)-DA and the catalytic amplification strategy of MOFCeAgNC on HAuCl4-SL, a sensitive and convenient DA platform for dual-mode detection of SERS and RRS is constructed. In addition, the platform is successfully applied to detect DA in human serum with satisfactory recoveries (95.7-102%).

A new Fe/N doped carbon dot naocatalytic amplification-aptamer SERS/RRS/Abs trimode assay platform for ultratrace Pb2.

Nanocatalytic amplification of carbon dots is a new way to improve sensitivity. The preparation of the high catalytic activity and stable iron/nitrogen-doped carbon dot (CDBFe) sol and its application in aptamer (Apt) assay have not been reported yet. In this paper, a simple hydrothermal procedure for the preparation of CDBFe derived from Fe2+-2,2'-bipyridine complex has been developed. It is found that CDBFe has a strong catalytic effect on the indicator reaction of glyoxal (C2H2O2) reduction of HAuCl4 to produce gold nanoparticle (AuNP) probe with strong surface enhanced Raman scattering (SERS) at 1617 cm-1, resonance Rayleigh scattering (RRS) effect at 370 nm and absorption (Abs) at 550 nm. A rapid and sensitive CDBFe catalytic amplification Apt method for SERS/RRS/Abs trimode detecting ultratrace lead ions was established, based on the Apt reaction mediated the nanocatalytic indicator reaction. The results show that the SERS intensity and Pb(II) concentration have a good linear relationship in the range of 1.3-16 pM, and the detection limit is the lowest. In addition, Hg(II) and As(III) can also be measured by this naocatalytic amplification- Apt assay platform.