Visible Region Research Articles

Portable Near-Infrared to Near-Infrared Platform for Homogeneous Quantification of Biomarkers in Complex Biological Samples.

Förster resonance energy transfer (FRET)-based homogeneous immunoassay obviates tedious washing steps and thus is a promising approach for immunoassays. However, a conventional FRET-based homogeneous immunoassay operating in the visible region is not able to overcome the interference of complex biological samples, thus resulting in insufficient detection sensitivity and poor accuracy. Here, we develop a near-infrared (NIR)-to-NIR FRET platform (Ex = 808 nm, Em = 980 nm) that enables background-free high-throughput homogeneous quantification of various biomarkers in complex biological samples. This NIR-to-NIR FRET platform is portable and easy to operate and is mainly composed of a high-performance NIR-to-NIR FRET pair based on lanthanide-doped nanoparticles (LnNPs) and a custom-made microplate reader for readout of NIR luminescence signals. We demonstrate that this NIR-to-NIR FRET platform is versatile and robust, capable of realizing highly sensitive and accurate detection of various critical biomarkers, including small molecules (morphine and 1,25-dihydroxyvitamin D), proteins (human chorionic gonadotropin), and viral particles (adenovirus) in unprocessed complex biological samples (urine, whole blood, and feces) within 5-10 min. We expect this NIR-to-NIR FRET platform to provide low-cost healthcare for populations living in resource-limited areas and be widely used in many other fields, such as food safety and environmental monitoring.

Synthesis, structural, spectroscopic and theoretical insights into a new malononitrile derivative: A candidate for nonlinear optical applications

Functionalized alkylidene malononitriles play a crucial role as donor-acceptor molecules, exhibiting notable nonlinear optical (NLO) properties. Allylidene malononitriles, an analogue of alkylidene malononitriles, have not been explored before for their optical properties. The present work deals with the synthesis of (Z)-2-(3-(4-bromophenyl)-3-chloroallylidene) malononitrile using Knoevenagel condensation reaction of Z-3-(4-bromophenyl)-3-chloroacrylaldehyde and malononitrile. Structure of the compound was elucidated by single-crystal X-ray crystallography and related spectroscopic studies like FT-IR, NMR (1H, 13C), and UV–Vis spectroscopy, which were further supported with computational studies using Density Functional Theory (DFT) approach. The photoluminescence spectra showed that the compound exhibited an emission peak at 425 nm with an excitation wavelength of 352 nm. The single crystal study reveals that the compound belongs to a monoclinic system with space group P21/c. The thermal characteristics of the compound was analysed using TGA-DTA/DSC. Investigation of the third-order nonlinear susceptibility was done by femtosecond Z-scan technique and demonstrated the potential of phenyl-substituted allylidene malononitriles for its nonlinear optical applications. The observed positive lensing and strong reverse saturable absorption (RSA) at both visible (532 nm) and Near IR (800 nm) regions make this compound a promising candidate for optoelectronic applications.

Synthesis of CuO nanosheets on Cu foil via one-step wet chemical process at different reaction temperatures and their photoelectrochemical performance

Cupric oxide (CuO) nanostructures were directly grown on copper substrate via a simple one step solution-immersion process. The films were formed by the direct oxidation of copper in aqueous solution containing sodium hydroxide (NaOH) and ammonium persulfate (NH4)2S2O8. The influence of the reaction temperature on the structural, morphological, optical and photoelectrochemical (PEC) properties of the formed copper compounds nanostructures was investigated. The XRD and Raman spectroscopy results revealed the formation of Cu(OH)2/CuO composite for the samples prepared at 3 and 25 °C, and pure CuO was obtained for the samples prepared at 45 and 55 °C. The SEM micrographs showed that the formed Cu(OH)2 and CuO present a nanowire bundles and nanosheet morphology, respectively. The increase of the reaction temperature enhanced the absorbance of the CuO samples in the entire visible region. According to the photoelectrochemical measurements, the increase of the reaction temperature resulted in an improvement of the PEC response. The CuO nanosheets synthesized at 55 °C presents the highest and the most stable PEC response. A reasonable mechanism describing the formation of nanostructured copper compounds at different reaction temperatures is discussed in this paper.

Colloidal TiO2 nanocrystals with engineered defectivity and optical properties.

Partially reduced forms of titanium dioxide (sometimes called "black" titania) have attracted widespread interest as promising photocatalysts of oxidation due to their absorption in the visible region. The main approaches to produce it rely on postprocessing at high temperatures (up to 800 °C) and high pressures (up to 40 bar) or on highly reactive precursors (e.g., TiH2), and yield powders with poorly controlled sizes, shapes, defect concentrations and distributions. We describe an approach for the one-step synthesis of TiO2 colloidal nanocrystals at atmospheric pressure and temperatures as low as 280 °C. The temperature of the reaction allows the density of oxygen vacancies to be controlled by nearly two orders of magnitude independently of their size, shape, or colloidal stability. This synthetic pathway appears to produce vacancies that are homogeneously distributed in the nanocrystals, rather than being concentrated in an amorphous shell. As a result, the defects are protected from oxidation and result in stable optical properties in oxidizing environments.

Enhanced Fluorescence Based on Slow Light Effect of ZIF-8 Photonic Crystals for Trace 2,4,6-Trinitrophenol Detection.

In response to growing concerns about public safety and environmental conservation, it is essential to develop a precise identification method for trace explosives. To improve the stability and detection sensitivity of perovskite quantum dots (PQDs) and address the issue of low porosity in traditional polymer-based photonic crystals (PhCs), this study proposed a PQD photoluminescence (PL) enhancement strategy based on the slow light effect of ZIF-8 PhCs for highly sensitive, selective, and convenient detection of 2,4,6-trinitrophenol (TNP). The slow light effect at the photonic band gap edge is the basis of amplifying the PL signal. PhCs were fabricated by the evaporation-induced self-assembly method. The diffraction wavelength overlapping the whole visible region was designed to match the emission wavelength of PQDs. Results showed that PhCs matching the PBG edge with PQDs' emission peak amplified the PL signal 11.3 times, significantly improving sensitivity for trace TNP detection with a limit as low as 2.52 nM. Moreover, there was a 13.3-fold enhancement of PQDs' fluorescence lifetime when the emission wavelength fell in the PBG range. The hydrophobic surface of ZIF-8 PhCs enhanced the PQDs' stability and moisture resistance. Furthermore, the selective quenching mechanism of TNP by the sensor was photoinduced electron transfer (PET) verified by DFT calculations and time-resolved PL decay dynamics measurements. This study demonstrated great potential for manipulating light emission enhancement by PhCs in developing efficient fluorescent sensors for trace environmental pollutant detection.

Introduction of Electron Donor Groups into the Azulene Structure: The Appearance of Intense Absorption and Emission in the Visible Region.

In this work, through the Suzuki-Miyaura cross-coupling reaction with high yields, new π-conjugated azulene compounds containing diphenylaniline groups at positions 2 and 6 of azulene were synthesized. The obtained diphenylaniline-azulenes have intensely visible-light absorbing and emitting (in the wavelength range from 400 to 600 nm) properties. It has been shown that such unique optical properties, in particular fluorescent emission in the region of blue and green photoluminescence (λem at 495 and 525 nm), which were absent in the original azulene, are the result of the electron donor effect of diphenylaniline groups, which significantly changes the electronic structure of azulene and leads to the allowed HOMO → LUMO electron transition.

Sol-Gel Synthesis of TiO2 with Pectin and Their Efficiency in Solar Cells Sensitized by Quantum Dots.

In this study, titanium oxide TiO2 nanoparticles were produced using the sol-gel approach of green synthesis with pectin as the reducing agent. The synthetized TiO2 nanoparticles with pectin were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), visible light absorption (UV-Vis) and the BET method. The structure and morphology of the TiO2 powder were described with SEM, revealing uniform monodisperse grains with a distribution of 80% regarding sizes < 250 nm; the resulting crystal phase of synthetized TiO2 was identified as an anatase and rutile phase with a crystallinity size estimated between 27 and 40 nm. Also, the surface area was determined by nitrogen adsorption-desorption using the Brown-Emmet-Teller method, with a surface area calculated as 19.56 m2/g, typical of an IV type isotherm, indicating mesoporous NPs. UV-Vis spectra showed that sol-gel synthesis reduced the band gap from the 3.2 eV common value to 2.22 eV after estimating the optical band gap energy using the adsorption coefficient; this translates to a possible extended photo response to the visible region, improving photoactivity. In addition, the power conversion of the photoelectrode was compared based on similar assembly techniques of TiO2 electrode deposition. Quantum dot crystals were deposited ionically on the electrode surface, as two different paste formulations based on a pectin emulsifier were studied for layer deposition. The results confirm that the TiO2 paste with TiO2-synthesized powder maintained good connections between the nanocrystalline mesoporous grains and the deposited layers, with an efficiency of 1.23% with the transparent paste and 2.27% with the opaque paste. These results suggest that pectin could be used as a low-cost, functional sol-gel catalysis agent for the synthesis of controlled NPs of metal oxide. It demonstrates interesting optical properties, such as an increase in photo response, suggesting further applications to photocatalysts and biomedical features.

Extra-Annulated Chlorophyll Derivatives by Scholl Reaction.

The ferric chloride assisted Scholl reaction of methyl (3,5-dimethoxyphenyl)carbonyl-pyropheophorbide-a produced an extra-annulated, didehydrogenated chlorophyll derivative with a six-membered ring fused at the pyrrole A-ring. The steric interaction of the substituents on the additional tetralone and B-rings induced molecular helicity. The helically cyclized stereoisomers were separated by recrystallization, and their (P/M)-stereochemistry was confirmed by circular dichroism spectra. The distortion of their chlorin π-systems broadened electronic absorption bands to cover all visible regions and reach the near-infrared region.

Intrinsic Chiroptical Activity and Excitonic Properties of Group II-VI Magic-Size Clusters.

Semiconductor magic-size clusters (MSCs), lying in the local minima of the potential landscape, are important intermediates that emerge during the synthesis of colloidal quantum dots. They have definite geometrical and electronic structures, thus serving as atomically precise building blocks for assembling supramolecular structures and devices with unprecedented functionalities. Here we report the intrinsic chiroptical activity in the magic-size cadmium and zinc chalcogenide clusters with magic numbers of 13, 33, and 34 possessing unique core-shell structures. They are responsive to circularly polarized light from the ultraviolet to visible region, with size-tunable energy gap, absorption wavelength, and excitonic characteristics. The origin of the chiroptical activity and the evolution of excitonic states with magic size are disclosed by time-dependent density functional theory calculations within a correlated electron-hole picture. This molecular-level understanding of the photophysical properties of group II-VI MSCs provides essential guidelines for utilizing them for chiral optoelectronics and photonics.

Novel TiO2-Supported Gold Nanoflowers for Efficient Photocatalytic NOx Abatement.

In this study, we pioneered the synthesis of nanoflower-shaped TiO2-supported Au photocatalysts and investigated their properties. Au nanoflowers (Au NFs) were prepared by a Na-citrate and hydroquinone-based preparation method, followed by wet impregnation of the derived Au NFs on the surface of TiO2 nanorods (TNR). A uniform and homogeneous distribution of Au NFs was observed in the TNR + NF(0.7) sample (lower Na-citrate concentration), while their distribution was heterogeneous in the TNR + NF(1.4) sample (higher Na-citrate concentration). The UV-Vis DR spectra revealed the size- and shape-dependent optical properties of the Au NFs, with the LSPR effect observed in the visible region. The solid-state EPR spectra showed the presence of Ti3+, oxygen vacancies and electron interactions with organic compounds on the catalyst surface. In the case of the TNR + NF(0.7) sample, high photocatalytic activity was observed in the H2-assisted reduction of NO2 to N2 at room temperature under visible-light illumination. In contrast, the TNR + NF(1.4) catalyst as well as the heat-treated samples showed no ability to reduce NO2 under visible light, indicating the presence of deformed Au NFs limiting the LSPR effect. These results emphasized the importance of the choice of synthesis method, as this could strongly influence the photocatalytic activity of the Au NFs.

Serendipitous Discovery of Conjugated Dipyrromethene-Linked Nitronaphthoporphyrins.

Acid-catalyzed condensation of a nitronaphthalene-fused dipyrrylmethane with dipyrrylmethane dialdehydes afforded unique dipyrromethene-naphthoporphyrin conjugates together with expected nitronaphthoporphyrins. The unusual conjugated system retained aromatic porphyrin-type characteristics but afforded highly modified UV-vis spectra with multiple absorptions throughout the visible region.

Ion Implantation‐Induced Bandgap Modifications in the ALD TiO2 Thin Films

Atomic layer deposited (ALD) TiO2 layers are implanted with N, O, and Ar ions to reduce the bandgap, thereby increasing its absorbance in the visible region. The implantation is accomplished with 40 keV nitrogen, 45 keV oxygen, and 110 keV argon ions in the fluence range 1 × 1015 to 5.6 × 1016 ions cm−2. The energy of each incident ion is tuned using stopping and range of ions in matter (SRIM) to produce defects around the same projected range. The structural analysis of the as‐deposited film is performed through X‐ray diffraction (XRD), scanning electron microscopy (SEM), Rutherford backscattering (RBS), and time of flight elastic recoil detection analysis (ToF‐ERDA). The implanted layers are characterized using diffuse reflectance spectroscopy (DRS) and Fourier transform infrared spectroscopy (FTIR) to study the optical and vibrational properties of the films. The results demonstrate that nitrogen implantation in TiO2 reduces the reflectance from 43.52% to 26.31% and bandgap from 2.68 to 2.61 eV, making it a promising bandgap‐engineered material for capping layers in solar cell applications. The refractive index of the 40 keV nitrogen ion implanted film at 1 × 1016 ions cm−2 (N‐16) increases from ≈2.8 to ≈2.95. OPAL2 solar cell simulations show that the N‐16 implanted TiO2 anti‐reflective coatings (ARC) can enhance the absorbed photocurrent by 7.3%.

Dihydropyridopyrazine Functionalized Xanthene: Generating Stable NIR Dyes with Small-Molecular Weight by Enhanced Charge Separation.

Near-infrared region (NIR; 650-1700 nm) dyes offer many advantages over traditional dyes with absorption and emission in the visible region. However, developing new NIR dyes, especially organic dyes with long wavelengths, small molecular weight, and excellent stability and biocompatibility, is still quite challenging. Herein, we present a general method to enhance the absorption and emission wavelengths of traditional fluorophores by simply appending a charge separation structure, dihydropyridopyrazine. These novel NIR dyes not only exhibited greatly redshifted wavelengths compared to their parent dyes, but also displayed a small molecular weight increase together with retained stability and biocompatibility. Specifically, dye NIR-OX, a dihydropyridopyra-zine derivative of oxazine with a molecular mass of 386.2 Da, exhibited an absorption at 822 nm and an emission extending to 1200 nm, making it one of the smallest molecular-weight NIR-II emitting dyes. Thanks to its rapid metabolism and long wave-length, NIR-OX enabled high-contrast bioimaging and assessment of cholestatic liver injury in vivo and also facilitated the evalua-tion of the efficacy of liver protection medicines against cholestatic liver injury.

Dihydropyridopyrazine Functionalized Xanthene: Generating Stable NIR Dyes with Small‐Molecular Weight by Enhanced Charge Separation

Near‐infrared region (NIR; 650–1700 nm) dyes offer many advantages over traditional dyes with absorption and emission in the visible region. However, developing new NIR dyes, especially organic dyes with long wavelengths, small molecular weight, and excellent stability and biocompatibility, is still quite challenging. Herein, we present a general method to enhance the absorption and emission wavelengths of traditional fluorophores by simply appending a charge separation structure, dihydropyridopyrazine. These novel NIR dyes not only exhibited greatly redshifted wavelengths compared to their parent dyes, but also displayed a small molecular weight increase together with retained stability and biocompatibility. Specifically, dye NIR‐OX, a dihydropyridopyra‐zine derivative of oxazine with a molecular mass of 386.2 Da, exhibited an absorption at 822 nm and an emission extending to 1200 nm, making it one of the smallest molecular‐weight NIR‐II emitting dyes. Thanks to its rapid metabolism and long wave‐length, NIR‐OX enabled high‐contrast bioimaging and assessment of cholestatic liver injury in vivo and also facilitated the evalua‐tion of the efficacy of liver protection medicines against cholestatic liver injury.

MoSSe/Si9C15 heterojunction photodetectors with ultrahigh photocurrent and carrier mobility

The structural, electronic, optical properties and photogalvanic effect of MoSSe/Si9C15 and Si9C15/MoSSe heterostructures are investigated utilizing density functional theory. Band gaps of 1.70 eV and 1.03 eV are respectively exhibited by these heterostructures, both classified as direct bandgap semiconductors. The thermal stability of the MoSSe/Si9C15 and Si9C15/MoSSe heterostructures is demonstrated through ab initio molecular dynamics calculations. A hole mobility of 62774 cm2/Vs in the zigzag direction and an electron mobility of 1248 cm2/Vs in the armchair direction are recorded for the MoSSe/Si9C15 heterostructure. Light absorption in both the ultraviolet and visible light regions is observed for these heterostructures. Upon construction of a self-powered MoSSe/Si9C15 photodetector, a peak photocurrent (Jph) of 10.76 a02/photon is achieved, influenced by changes in polarization angle θ and photon energy, and a maximum extinction ratio of 26.7 is reached, showcasing high polarization sensitivity.

Complexes of a piperazine based macrocycle as Cu-Zn SOD biomimetic: approach by constants determination

Obtaining new compounds capable of catalyzing the dismutation reaction of the superoxide anion carried out by the enzyme Cu,Zn-SOD has become a topic of great interest. In the present work, the study of a ligand with a piperazine fragment and its Cu(II) and Zn(II) complexes is introduced. The protonation constants of the ligand, the stability constants of the complex species un with equivalent of Cu(II) and Zn(II), forming both mononuclear and heterobinuclear species, in the presence and absence of histidine as secondary ligand were determined. For all cases, species distribution diagrams were obtained, from which the spectra in the visible region of the species of greatest interest were obtained. As an approach to the Cu,Zn-SOD system, the formation of quaternary species formed between these ions, the main ligand and histidine as a secondary ligand, was verified, which could be used as mimetics of said enzyme. Some theoretical studies were carried out to support this study.

Achieving Ultra-Broadband Sunlight-Like Emission in Single-Phase Phosphors: The Interplay of Structure and Luminescence.

The quest for artificial light sources mimicking sunlight has been a long-standing endeavor, particularly for applications in anticounterfeiting, agriculture, and color hue detection. Conventional sunlight simulators are often cost-prohibitive and bulky. Therefore, the development of a series of single-phase phosphors Ca9LiMg1-xAl2x/3(PO4)7:0.1Eu2+ (x = 0-0.75) with sunlight-like emission represents a welcome step towards compact and economical light source alternatives. The phosphors are obtained by an original heterovalent substitution method and emit a broad spectrum spanning from violet to deep red. Notably, the phosphor with x = 0.5 exhibits an impressive full width at half-maximum of 330nm. A synergistic interplay of experimental investigations and theory unveils the mechanism behind sunlight-like emission due to the local structural perturbations introduced by the heterovalent substitution of Al3+ for Mg2+, leading to a varied distribution of Eu2+ within the lattice. Subsequent characterization of a series of organic dyes combining absorption spectroscopy with convolutional neural network analysis convincingly demonstrates the potential of this phosphor in portable photodetection devices. Broad-spectrum light source testing empowers the model to precisely differentiate dye patterns. This points to the phosphor being ideal for mimicking sunlight. Beyond this demonstrated application, the phosphor's utility is envisioned in other relevant domains, including visible light communication and smart agriculture.

First Principle calculations for structural and optoelectronic properties of MnNi1-xAgxGe alloys: A DFT study

We investigate the optical and electronic characteristics of parental MnNiGe and doped MnNi1-xAgxGe (x = 4 %, 8 %, and 12 %) for photodetector and other electronic applications. First principles are applied to every calculation performed in the context of DFT. The generalized gradient approximation with the Hubbard potential included (GGA + U) has been chosen as the appropriate approximation to handle systems with strongly coupled electrons. The semi-metallic parental MnNiGe and doped MnNi1-xAgxGe (x = 4 %, 8 %, and 12 %) is ideal for conducting materials in electronics due to band overlapping, according to our findings. Degenerate doping of Ag into MnNiGe includes spinning the Fermi level, changing the DOS profile, and reducing the density of Fermi level states that allow tunneling from the valence band to the conduction band. An important part of this research is analyzing the refractive index, reflectivity, extinction coefficient, dielectric function, absorption coefficient, and energy loss function of parental MnNiGe and doped MnNi1-xAgxGe (x = 4 %, 8 %, and 12 %). According to our findings, it is possible to create a photo detector based on MnNi1-xAgxGe (x = 4 %, 8 %, and 12 %) that can detect light in the visible range (below 500 nm). It has also been found that the MnNi1-xAgxGe (x = 4 %, 8 %, and 12 %) exhibits the highest sensitivity to light with a wavelength of 450 nm. Due to its advantageous optical characteristics in the visible and ultraviolet regions, this material could be useful for the development of numerous optoelectronic applications.

Near-infrared imaging via upconversion in Er3+:CaF2 crystal with dual wavelength excitation.

We propose a system for imaging 1510 nm near-infrared (NIR) wavelength via upconversion (UC) luminescence in an Er3+-doped CaF2 crystal. Er3+ ions are excited from the ground to the excited state levels by an 800-nm pre-excitation wavelength, followed by the promotion of these ions to a higher energy level by the NIR excitation wavelength. Relaxation of these excited ions gives rise to 540 nm UC luminescence in the visible region, enabling the detection of the 1510 nm NIR wavelength. Using this UC scheme, 1510 nm was successfully imaged. Our system enables imaging of NIR wavelengths using low-cost optics and readily available Si-based detectors that are sensitive only to visible wavelengths, opening new possibilities for detection and imaging of NIR wavelengths.

Universal hydrogel adhesives with robust chain entanglement for bridging soft electronic materials

Ensuring stable integration of diverse soft electronic components for reliable operation under dynamic conditions is crucial. However, integrating soft electronics, comprising various materials like polymers, metals, and hydrogels, poses challenges due to their different mechanical and chemical properties. This study introduces a dried-hydrogel adhesive made of poly(vinyl alcohol) and tannic acid multilayers (d-HAPT), which integrates soft electronic materials through moisture-derived chain entanglement. d-HAPT is a thin (~1 µm) and highly transparent (over 85% transmittance in the visible light region) adhesive, showing robust bonding (up to 3.6 MPa) within a short time (<1 min). d-HAPT demonstrates practical application in wearable devices, including a hydrogel touch panel and strain sensors. Additionally, the potential of d-HAPT for use in implantable electronics is demonstrated through in vivo neuromodulation and electrocardiographic recording experiments while confirming its biocompatibility both in vitro and in vivo. It is expected that d-HAPT will provide a reliable platform for integrating soft electronic applications.