The Difference between Plasmon Excitations in Chemically Heterogeneous Gold and Silver Atomic Clusters.

Weak doping can broaden, shift, and quench plasmon peaks in nanoparticles, but the mechanistic intricacies of the diverse responses to doping remain unclear. In this study, we used the time-dependent density functional theory (TD-DFT) to compute the excitation properties of transition-metal Pd- or Pt-doped gold and silver atomic arrays and investigate the evolution characteristics and response mechanisms of their plasmon peaks. The results demonstrated that the Pd or Pt doping of the off-centered 10 × 2 atomic arrays broadened or shifted the plasmon peaks to varying degrees. In particular, for Pd-doped 10 × 2 Au atomic arrays, the broadened plasmon peak significantly blueshifted, whereas a slight red shift was observed for Pt-doped arrays. For the 10 × 2 Ag atomic arrays, Pd doping caused almost no shift in the plasmon peak, whereas Pt doping caused a substantial red shift in the broadened plasmon peak. The analysis revealed that the diversity in these doping responses was related to the energy positions of the d electrons in the gold and silver atomic clusters and the positions of the doping atomic orbitals in the energy bands. The introduction of doping atoms altered the symmetry and gap size of the occupied and unoccupied orbitals, so multiple modes of single-particle transitions were involved in the excitation. An electron transfer analysis indicated a close correlation between excitation energy and the electron transfer of doping atoms. Finally, the differences in the symmetrically centered 11 × 2 doped atomic array were discussed using electron transfer analysis to validate the reliability of this analytical method. These findings elucidate the microscopic mechanisms of the evolution of plasmon peaks in doped atomic clusters and provide new insights into the rational control and application of plasmons in low-dimensional nanostructures.

Recent advances in ternary Z-scheme photocatalysis on graphitic carbon nitride based photocatalysts.

Due to its excellent photocatalytic performance over the last few years, graphitic-like carbon nitride (g-C3N4) has garnered considerable notice as a photocatalyst. Nevertheless, several limitations, including small surface area, the rates at which photo-generated electrons and holes recombine are swift, and the inefficient separation and transport of photoexcited carriers continue to impede its solar energy utilization. To overcome those limitations in single-component g-C3N4, constructing a heterogeneous photocatalytic system has emerged as an effective way. Among the various studies involving the incorporation of hetero composite materials to design heterojunctions, among the most promising approaches is to assemble a Z-scheme photocatalytic configuration. The Z-scheme configuration is essential because it facilitates efficient photocarrier separation and exhibits superior redox ability in separated electrons and holes. Moreover, ternary composites have demonstrated enhanced photocatalytic activities and reinforced photostability. Ternary Z-scheme heterostructures constructed with g-C3N4 possess all the above-mentioned merits and provide a pioneering strategy for implementing photocatalytic systems for environmental and energy sustainability. A summary of the latest technological advancements toward design and fabrication in ternary all-solid-state Z-scheme (ASSZ) and direct Z-scheme (DZ) photocatalysts built on g-C3N4 is presented in this review. Furthermore, the review also discusses the application of ternary Z-scheme photocatalytic architecture established on g-C3N4.

High-performance and self-powered photodetectors from an S-scheme Cs2SnI2Cl2/Cs2TiI6 heterojunction: a DFT+NAMD study.

The recently reported two-dimensional (2D) Ruddlesden-Popper perovskite materials exhibit a plethora of advantages, making them an ideal candidate for constructing high-performance photodetectors. The mixed 2D/3D Cs2SnI2Cl2/Cs2TiI6 heterojunction is an S-scheme heterojunction and has excellent light trapping ability. Due to the spontaneous transfer of carriers caused by different work functions, a built-in electric field is formed in the heterojunction and the self-powered capability is provided. Through the nonadiabatic molecular dynamics (NAMD) method, it is found that the heterojunction exhibits fast photoresponse, low losses and efficient carrier separation. In addition, biaxial compressive strain can not only broaden the photoresponse of the Cs2SnI2Cl2/Cs2TiI6 heterojunction in the near-infrared region and enhance the optical absorption coefficient of the heterojunction, but also enhance the self-powered ability of the heterojunction. Our discoveries present a highly effective avenue for the future development of high-performance, self-powered hybrid optoelectronic devices.

Polyhedral Au Nanoparticle/MoOx Heterojunction-Enhanced Ultrasensitive Dual-Mode Biosensor for miRNA Detection Combined with a Nonenzymatic Cascade DNA Amplification Circuit.

A novel homologous surface-enhanced Raman scattering (SERS)-electrochemical (EC) dual-mode biosensor based on a 3D/2D polyhedral Au nanoparticle/MoOx nanosheet heterojunction (PAMS HJ) and target-triggered nonenzyme cascade autocatalytic DNA amplification (CADA) circuit was constructed for highly sensitive detection of microRNA (miRNA). Mixed-dimensional heterostructures were prepared by in situ growth of polyhedral Au nanoparticles (PANPs) on the surface of MoOx nanosheets (MoOx NSs) via a seed-mediated growth method. As a detection substrate, the resulting PAMS HJ shows the synergistic effects of both electromagnetic and chemical enhancements, efficient charge transfer, and robust stability, thus achieving a high SERS enhancement factor (EF) of 4.2 × 109 and strong EC sensing performance. Furthermore, the highly efficient molecular recognition between the target and smart lock probe and the gradually accelerated cascade amplification reaction further improved the selectivity and sensitivity of our sensing platform. The detection limits of miRNA-21 in SERS mode and EC mode were 0.22 and 2.69 aM, respectively. More importantly, the proposed dual-mode detection platform displayed excellent anti-interference and accuracy in the analysis of miRNA-21 in human serum and cell lysates, indicating its potential as a reliable tool in the field of biosensing and clinical analysis.

Ultrathin MXene nanosheet-based TiO2/CdS heterostructure as a photoelectrochemical sensor for detection of CEA in human serum samples.

To develop highly accurate and ultrasensitive strategies is of great importance for the clinical measurement, in particular, the detection of cancer biomarkers. Herein, we synthesized an ultrasensitive TiO2/MXene/CdS QDs (TiO2/MX/CdS) heterostructure as a photoelectrochemical immunosensor, which favors energy levels matching and fast electron transfer from CdS to TiO2 in the help of ultrathin MXene nanosheet. Dramatic photocurrent quenching can be observed upon incubation of the TiO2/MX/CdS electrode by Cu2+ solution from 96-well microplate, which caused by the formation of CuS and subsequent CuxS (x = 1, 2), reducing the absorption of light and boosting the electron-hole recombination upon irradiation. As a result, the as-prepared biosensor demonstrates a linearly increased photocurrent quenching percentage (Q%) value with CEA concentration ranging from 1 fg/mL to 10 ng/mL, as well as a low detection limit of 0.24 fg/mL. Benefit from its excellent stability, high selectivity and good reproducibility of as-prepared PEC immunosensor, we believe that this proposed strategy might provide new opportunities for clinical diagnosis of CEA and other tumor markers.

Reactive Flame-Retardant Cotton Fabric Coating: Combustion Behavior, Durability, and Enhanced Retardant Mechanism with Ion Transfer.

In recent years, we have witnessed numerous indoor fires caused by the flammable properties of cotton. Flame-retardant cotton deserves our attention. A novel boric acid and diethylenetriaminepenta (methylene-phosphonic acid) (DTPMPA) ammonium salt-based chelating coordination flame retardant (BDA) was successfully prepared for cotton fabrics, and a related retardant mechanism with ion transfer was investigated. BDA can form a stable chemical and coordination bond on the surface of cotton fibers by a simple three-curing finishing process. The limiting oxygen index (LOI) value of BDA-90 increased to 36.1%, and the LOI value of cotton fabric became 30.3% after 50 laundering cycles (LCs) and exhibited excellent durable flame retardancy. Fourier-transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) methods were used to observe the bonding mode and morphology of BDA on cotton fibers. A synergistic flame-retardant mechanism of condensed and gas phases was concluded from thermogravimetry (TG), cone calorimeter tests, and TG-FTIR. The test results of whiteness and tensile strength showed that the physical properties of BDA-treated cotton fabric were well maintained.

Sc/C codoping effect on the electronic and optical properties of the TiO2 (101) surface: a first-principles study.

Extension of the light absorption range and a reduction of the possibility of the photo-generated electron-hole pair recombination are the main tasks to break the bottleneck of the photocatalytic application of TiO2. In this paper, we systematically investigate the electronic and optical properties of Sc-doped, C-doped, and Sc/C-codoped TiO2 (101) surfaces using spin-polarized DFT+U calculations. The absorption coefficient of the Sc/C-codoped TiO2 (101) surfaces were enhanced the most compared with the other two doped systems in the high energy region of visible light, which can be attributed to the shallow impurity states. Furthermore, we studied the optical absorption properties with the change of the impurity concentration. The Sc/C-codoped TiO2 (101) surface with 5.56% impurity concentration exhibited optimal photocatalytic performance in the visible region. These results may be helpful for designing the high-performance of the photocatalysts by doping.

Superhydrophilicity and strong salt-affinity: Zwitterionic polymer grafted surfaces with significant potentials particularly in biological systems.

In recent years, zwitterionic polymers have been frequently reported to modify various surfaces to enhance hydrophilicity, antifouling and antibacterial properties, which show significant potentials particularly in biological systems. This review focuses on the fabrication, properties and various applications of zwitterionic polymer grafted surfaces. The "graft-from" and "graft-to" strategies, surface grafting copolymerization and post zwitterionization methods were adopted to graft lots type of the zwitterionic polymers on different inorganic/organic surfaces. The inherent hydrophilicity and salt affinity of the zwitterionic polymers endow the modified surfaces with antifouling, antibacterial and lubricating properties, thus the obtained zwitterionic surfaces show potential applications in biosystems. The zwitterionic polymer grafted membranes or stationary phases can effectively separate plasma, water/oil, ions, biomolecules and polar substrates. The nanomedicines with zwitterionic polymer shells have "stealth" effect in the delivery of encapsulated drugs, siRNA or therapeutic proteins. Moreover, the zwitterionic surfaces can be utilized as wound dressing, self-healing or oil extraction materials. The zwitterionic surfaces are expected as excellent support materials for biosensors, they are facing the severe challenges in the surface protection of marine facilities, and the dense ion pair layers may take unexpected role in shielding the grafted surfaces from strong electromagnetic field.

Analysis of pesticide residues in commercially available chenpi using a modified QuEChERS method and GC-MS/MS determination.

To ensure the safety of the commercially available chenpi, a convenient and fast analytical method was developed for the determination of 133 pesticide residues in chenpi using gas chromatography-tandem mass spectrometry (GC-MS/MS). In this study, different extraction solvents, redissolution solvents and adsorbents were tested according to the recovery and purification effect to obtain a modified QuEChERS method. The samples were extracted with acetonitrile. During the clean-up step, octadecyl-modified silica (C18) and graphitized carbon black (GCB) were selected, and aminopropyl (NH2) was used instead of primary secondary amine (PSA) because of its weaker ion exchange capacity which had little effect on the recovery of ditalimfos. Samples were quantified by matrix-matched calibration with internal standards. All pesticides showed good linearity in the respective range, both with values of r 2 > 0.99. The average recoveries of the pesticides spiked samples ranged from 70.0% to 112.2% with the RSDs of 0.2%-14.4%. The modified QuEChERS method was validated and applied to twenty real samples. Five pesticides were found in eight batches, but no pesticide exceeded the maximum residue limits (MRL, MRL reference to European commission).

Construction of photonic crystals with thermally adjustable pseudo-gaps.

Photonic crystals (PCs) are periodic dielectric structures with photonic bandgaps and they can be used to control and manipulate photons effectively. Novel photonic crystal materials with tunable bandgaps can be prepared by changing the refractive index of the dielectric or lattice parameters under external stimuli, while using temperature to adjust the photonic band gap is a simple and convenient method. In this paper, silica PCs having different pseudo-gaps in the range of 450-750 nm were prepared with colloidal SiO2 spheres of different sizes. Thermo-sensitive PNIPAM hydrogel was then infiltrated into the PCs to obtain PNIPAM-PCs, whose pseudo-gap blue-shifted when the temperature was changed from 24 to 34 °C and exhibited good reversibility. The PCs with tunable bandgaps are significant for the development of integrated photonic devices, sensors, and in detection and other technologies.