Excited states of ortho-nitrobenzaldehyde as a challenging case for single- and multi-reference electronic structure theory.

We present a large set of vertical excitation calculations for the ortho-nitrobenzaldehyde (oNBA) molecule, which exhibits a very challenging excited-state electronic structure like other nitroaromatic compounds. The single-reference methods produce mostly consistent results up to about 5.5 eV. By contrast, the CAS second-order perturbation theory (CASPT2) results depend sensitively on the employed parameters. At the CAS self-consistent field level, the energies of the bright ππ * states are strongly overestimated while doubly excited states appear too low and mix with these ππ * states. This mixing hampers the CASPT2 step, leading to inconsistent results. Only by increasing the number of states in the state-averaging step to about 40-to cover all bright ππ * states embedded in the double excitations-and employing extended multistate CASPT2 could CASPT2 results consistent with experiment be obtained. We assign the four bands in the molecule's spectrum: The weakest band at 3.7 eV arises from the n NO 2 π * states, the second one at 4.4 eV from the ππ * ( L b ) state, the shoulder at 5.2 eV from the ππ * ( L a ) state, and the maximum at 5.7 eV from the ππ * ( B a / B b ) states. We also highlight the importance of modern wave function analysis techniques in elucidating the absorption spectrum of challenging molecules.

Spectroscopic and Spectroelectrochemical Studies of Hexapentyloxytriphenylene-A Model Discotic Molecule.

The electrochemical and spectroelectrochemical properties of the discotic mesogen 2,3,6,7,10,11-pentyloxytriphenylene (H5T) were studied with the use of cyclic voltammetry combined with UV-Vis and electron paramagnetic resonance (EPR) spectroscopy in solution. The UV-Vis absorption spectroscopy of H5T in dichloromethane showed its monomeric state in a concentration range up to 10-3 mol dm-3. The reversible process of the electrochemical formation of the radical cation was evidenced within the experimentally accessible potential window. The in situ UV-Vis spectroelectrochemical measurements further enabled identification of the product of the redox process and evaluation of the effect of aggregation in the concentration range of 5 × 10-3 mol dm-3. The results are discussed in the frame of solvent effects on the self-assembly propensity of solute molecules, in a wide range of concentrations. In particular, the crucial role of the solvent polarity is indicated, which contributes to the understanding of solution effects and pre-programming of supramolecular organic materials, in particular anisotropic disc-shaped hexa-substituted triphenylenes.

Effect of Solvent Polarity on the Spectral Characteristics of 5,10,15,20-Tetrakis(p-hydroxyphenyl)porphyrin.

The electronic absorption and vibrational spectra of deprotonated 5,10,15,20-tetrakis(p-hydroxyphenyl)porphyrin (THPP) are studied as a function of solvent polarity in H2O-DMF, H2O-acetone, H2O-methanol, and DMF-acetone mixtures. The maximum absorption wavelength (λmax) of the lowest energy electronic absorption band of deprotonated THPP shows an unusual solvatochromism-a bathochromic followed by a hypsochromic shift with reduced polarity. According to the correlation analysis, both specific interactions (H-bonds) and nonspecific interactions affect the spectral changes of this porphyrin. Furthermore, the solvent polarity scale ET(30) can explain both shifts very well. At higher polarity (ET(30) > 48), THPP exists as a hyperporphyrin. The ET(30) is linear with λmax and a decrease in solvent polarity is accompanied by a bathochromic shift of λmax. These results can be rationalized in terms of the cooperative effects of H-bonds and nonspecific interactions on the spectra of hyperporphyrin. At relatively low polarity (45.5 < ET(30) < 48), hyperporphyrin gradually becomes Na2P as ET(30) reaches the critical value of 45.5. The spectrum of the hyperporphyrin turns into the three-band spectrum of the metalloporphyrin, which is accompanied by a hypsochromic shift of λmax.

Rapid photodegradation of terrestrial soil dissolved organic matter (DOM) with abundant humic-like substances under simulated ultraviolet radiation.

Solar ultraviolet (UV) radiation exhibits a significant degradation for dissolved organic matter (DOM) in natural water ecosystems. However, research on photodegradation process of terrestrial components (e.g., humic-like substances) of DOM are limited due to drastic water dilution and rapid degradation. Here, photochemical degradation of terrestrial soil DOM with abundant humic-like substances from different land use were investigated by utilizing spectral technologies. Simulated UV radiation caused obvious losses on concentration, component structures, and fluorescence characteristic of soil DOM samples. The correlations between absorption specific parameters (a280, SUVA254, and SR) and dissolved organic carbon (DOC) were especially pronounced (p < 0.05), which could be used as valid indicators to determine changes in DOM composition and molecular size during photobleaching process. The decreases of DOM fluorescence intensity were corresponded to first-order kinetic and half-life reactions. The greatest reduction on fluorescence intensity (31.56-81.97%) belonged to peak C (i.e., humic-like substances). Overall, DOM from forest and grass soil ecosystems was more easily photochemical degraded than anthropogenic soil DOM. Enhancive contribution of fresh DOM formed by photodegradation increased autochthonous characteristic and bioavailable nutrition by increasing biological index (BIX) values and ammonia nitrogen (NH4+-N) concentration. The slight microbial decomposition effects on DOM happened in unsterilized dark condition. Our findings provided insights for understanding the rapid photodegradation processes of composition and structure of terrestrial DOM. Graphical abstract.

Comparative Study of the Interactions between Ovalbumin and five Antioxidants by Spectroscopic Methods.

L-Ascorbic acid, α-tocopherol, procyanidin B3, ß-carotene and astaxanthin are five classic dietary antioxidants. In this study, the interaction between the five antioxidants and ovalbumin was investigated by fluorescence spectroscopy, in combination with UV-vis absorption spectroscopy and circular dichroism (CD) spectroscopy. The quenching mechanism of ovalbumin by α-tocopherol is static quenching and the interaction between α-tocopherol and ovalbumin is synergistically driven by enthalpy and entropy. Electrostatic interactions and hydrophobic interactions play a major role in stabilizing the complex. For the other four antioxidants, the quenching mechanisms are all static quenching mechanisms at lower concentrations of antioxidants, but at higher concentrations of antioxidants, predominantly by the "sphere of action" quenching mechanisms. The binding processes of the other four antioxidants to ovalbumin are all entropy process and the major part of the action force is hydrophobic interactions. The binding constants of ovalbumin with the five antioxidants are in the following order as: astaxanthin > ß-carotene > L-ascorbic acid > procyanidin B3 > α-tocopherol at 298 K. Synchronous fluorescence spectroscopy shows the interaction between L-ascorbic acid/ß-carotene/astaxanthin and ovalbumin decreases the hydrophobicity of the microenvironment of tryptophan (Trp) and tyrosine (Tyr) residues. The hydrophobicity of Trp is increased while the hydrophility of Tyr is increased in the presence of α-tocopherol. However, the microenvironment of Trp and Tyr is not affected by procyanidin B3. The UV-vis absorption and CD spectra suggest that the interaction between the five antioxidants and ovalbumin leads to the loosening and unfolding of ovalbumin skeleton and exerts some influence on the natural secondary structure of ovalbumin. The study provides an accurate and full basic data for clarifying the binding mechanisms of L-ascorbic acid, α-tocopherol, procyanidin B3, ß-carotene and astaxanthin interacting with ovalbumin and is helpful for understanding rational use of antioxidants as dietary supplements.

Spectroscopic studies on the interaction of chromium (VI) and chromium (III) with keyhole limpet hemocyanin.

The interactions of keyhole limpet hemocyanin (KLH) with chromium nitrate, potassium dichromate, and chromate were investigated using fluorescence, UV-vis absorption and circular dichroism (CD) spectroscopy under simulated physiological conditions. The experimental results showed that the different forms of chromium could quench the intrinsic fluorescence of KLH following a static quenching mechanism rather than by dynamic collision, which indicated that a Cr-KLH complex was formed. The Stern-Volmer quenching constants for the interaction indicated that the binding reaction of KLH with Cr(VI) was stronger the binding of KLH with Cr(III). The thermodynamic values for binding of Cr(VI) to KLH are ΔH > 0 and ΔS > 0. By contrast, the values for the interaction of Cr(III) with KLH are ΔH < 0 and ΔS < 0. The results of synchronous fluorescence, UV-vis absorption and CD spectroscopy showed that the α-helical secondary structure and conformation of KLH were altered by different forms of chromium. Copyright © 2016 John Wiley & Sons, Ltd.

Spectroscopic Investigation of the Interaction of the Anticancer Drug Mitoxantrone with Sodium Taurodeoxycholate (NaTDC) and Sodium Taurocholate (NaTC) Bile Salts.

The focus of the present work was to investigate the interaction of the anticancer drug mitoxantrone with two bile salts, sodium taurodeoxycholate (NaTDC) and sodium taurocholate (NaTC). Ultraviolet-visible (UV-Vis) absorption and electron paramagnetic resonance (EPR) spectroscopy were used to quantify the interaction and to obtain information on the location of mitoxantrone in bile salt micelles. The presence of submicellar concentrations of both bile salts induces mitoxantrone aggregation and the extent of drug aggregation in NaTDC is higher than in NaTC. For micellar bile salts concentrations, mitoxantrone monomers are entrapped in the micellar core. Binding constants, micelle/water partition coefficients and the corresponding thermodynamic parameters for binding and partitioning processes were estimated using the changes in monomer absorbance in the presence of bile salts. Binding interaction of mitoxantrone is stronger for NaTDC than NaTC micelles, whereas partitioning efficiency is higher for NaTC micelles for all investigated temperatures. Thermodynamic parameters indicate that both binding and partitioning processes are spontaneous and entropy controlled. The spectral behavior and thermodynamic parameters indicate distinct types of mitoxantrone interaction with NaTDC and NaTC micelles supported by the differences in nature and structure of bile salts micelles.

Structural and biochemical properties of LuxF from Photobacterium leiognathi.

The lux-operon of bioluminescent bacteria contains the genes coding for the enzymes required for light emission. Some species of Photobacteria feature an additional gene, luxF, which shows similarity to luxA and luxB, the genes encoding the heterodimeric luciferase. Isolated dimeric LuxF binds four molecules of an unusually derivatized flavin, i.e., 6-(3'-(R)-myristyl)-FMN (myrFMN). In the present study we have heterologously expressed LuxF in Escherichia coli BL21 in order to advance our understanding of the protein's binding properties and its role in photobacterial bioluminescence. Structure determination by X-ray crystallography confirmed that apo-LuxF possesses four preorganized binding sites, which are further optimized by adjusting the orientation of amino acid side chains. To investigate the binding properties of recombinant LuxF we have isolated myrFMN from Photobacterium leiognathi S1. We found that LuxF binds myrFMN tightly with a dissociation constant of 80±20 nM demonstrating that the purified apo-form of LuxF is fully competent in myrFMN binding. In contrast to LuxF, binding of myrFMN to luciferase is much weaker (Kd=4.0±0.4 µM) enabling LuxF to prevent inhibition of the enzyme by scavenging myrFMN. Moreover, we have used apo-LuxF to demonstrate that myrFMN occurs in all Photobacteria tested, irrespective of the presence of luxF indicating that LuxF is not required for myrFMN biosynthesis.

Using resonance light scattering and UV/vis absorption spectroscopy to study the interaction between gliclazide and bovine serum albumin.

At different temperatures (298, 310 and 318 K), the interaction between gliclazide and bovine serum albumin (BSA) was investigated using fluorescence quenching spectroscopy, resonance light scattering spectroscopy and UV/vis absorption spectroscopy. The first method studied changes in the fluorescence of BSA on addition of gliclazide, and the latter two methods studied the spectral change in gliclazide while BSA was being added. The results indicated that the quenching mechanism between BSA and gliclazide was static. The binding constant (Ka ), number of binding sites (n), thermodynamic parameters, binding forces and Hill's coefficient were calculated at three temperatures. Values for the binding constant obtained using resonance light scattering and UV/vis absorption spectroscopy were much greater than those obtained from fluorescence quenching spectroscopy, indicating that methods monitoring gliclazide were more accurate and reasonable. In addition, the results suggest that other residues are involved in the reaction and the mode 'point to surface' existed in the interaction between BSA and gliclazide. Copyright © 2015 John Wiley & Sons, Ltd.

Effects of Cu on the content of chlorophylls and secondary metabolites in the Cu-hyperaccumulator lichen Stereocaulon japonicum.

Understanding the relationship between Cu and Cu-hyperaccumulator lichens is important for their application in monitoring and assessing heavy metal pollution. We investigated the Cu-hyperaccumulator lichen Stereocaulon japonicum at several Cu-polluted and control sites in Japan, and found the lichen to be widely distributed. Its concentrations of Cu, chlorophylls, and secondary metabolites, chlorophyll-related indices, and absorption spectra were measured, and we observed negative effects of Cu on these concentrations and indices. For highly Cu-polluted samples (>100ppm dry weight), however, we found significant linear correlations between Cu and chlorophyll concentrations. This can be considered as the response of the photobiont in S. japonicum to Cu stress. In highly Cu-polluted samples the chlorophyll-related indices and concentration of total secondary metabolites were almost constant regardless of Cu concentration. This suggests that the increase in chlorophyll concentration with the increase in Cu concentration enhances photosynthetic productivity per unit biomass, which will allow the production of extra structure and energy for maintaining the chlorophyll-related indices under Cu stress. The relationship between the increase in chlorophyll concentration of S. japonicum and the decrease in secondary metabolite concentration of the lichen can be explained by considering the balance of carbohydrates in the lichen. We found that a spectral index A372-A394 can be a useful index of the concentrations of Cu and total secondary metabolites in S. japonicum. These findings show the adjustment of the content of chlorophylls and secondary metabolites in S. japonicum to Cu stress, and provide a better understanding of the relationship between Cu and the Cu-hyperaccumulator lichen.

Correlating the Photovoltaic Performance and Stability of the All-Small-Molecule Organic Solar Cells to Their Intermixed Phases Determined by Concentration-Dependent Ultraviolet-Visible Absorption Spectroscopy.

In addition to the donor-acceptor nano phases, the intermixed phase within the organic blends is crucial for the photovoltaic performance and stability of the bulk-heterojunction organic solar cells (OSCs). Here, the intermixed phase of a representative M-PhS:BTP-eC9 all-small-molecule organic solar cell was investigated by a concentration-dependent ultraviolet-visible (UV-vis) absorption spectroscopy method, where a shift of the absorption maximum wavelength was measured for the acceptor component with the increase of the acceptor concentration. The blend ratios of the acceptor to the donor in the intermixed phase, corresponding to the critical concentration for the formation of the acceptor nanophase (CAP), were determined to be 0.35, 0.20, and 0.15 for the as-cast, thermal annealing (TA), and the combined TA and solvent vapor annealing films. These results indicated that M-PhS and BTP-eC9 are kinetically well intermixed during spin coating, whereas TA and the following solvent annealing promote the crystallization of BTP-eC9 molecules out of the intermixed phase. The photovoltaic performance of the M-PhS:BTP-eC9 cells with different blend ratios was investigated. The formation of the BTP-eC9 nano phase in the blend film leads to stable VOC and fast increased JSC, which can be understood by the reduction of bimolecular charge recombination and the formation of electron transporting pathways within the photoactive layer. Similarly, the critical concentration for the formation of the donor phase was estimated to be 0.15 by measuring the stabilized VOC and increased JSC values of the cells with different donor blending ratios. More importantly, after a fast "burn-in" thermal degradation, the M-PhS:BTP-eC9 cell showed excellent thermal stability aging at 85 °C for over 1128 h, which is in good accordance with the unchanged intermixed phases measured by the UV-vis spectra of the annealed films. The current work demonstrates the feasibility of the spectroscopy method to investigate the intermixed phases for organic bulk-heterojunction solar cells and proves that all-small-molecule solar cells can be intrinsically very stable.

Discovery of ultra-weakly coupled ß-carotene J-aggregates by machine learning.

Carotenoid aggregates are omnipresent in natural world and can be synthesized in hydrophilic environments. Despite different types of carotenoid aggregates have been reported hitherto, the way to predict the formation of carotenoid aggregates, i.e. H- or J-aggregates, is still challenging. Here, for the first time, we established machine learning models that can predict the formation behavior of carotenoid aggregates. The models are trained based on a database containing different types of carotenoid aggregates reported in the literatures. With the help of these machine learning models, we found a series of unknown types of ß-carotene J-aggregates. These novel aggregates are ultra-weakly coupled and have absorption bands up to 700 nm, different from all the carotenoid aggregates reported previously. Our work demonstrates that the machine learning is a powerful tool to predict the formation behavior of carotenoid aggregates and can further lead into the discovery of new carotenoid aggregates for different applications.

Nitric and nitrous acid formation in plasma-treated water: Decisive role of nitrogen oxides (NOx=1-3).

Nitrogen fixation using low-temperature plasma, particularly in relation to plasma-treated water (PTW) and its chemical and physical properties, has received a renewed research focus. Dissolving highly concentrated nitrogen oxides (NOx = 1-3) generated by air discharge into water results in the formation of two aqueous oxiacids (nitrous and nitric acids; HNOy = 2,3) and their conjugates (nitrate and nitrite ions; NOy-). Nonlinear formation of these species in PTW with respect to plasma conditions has been observed; however, the significance of the time-varying NOx on this nonlinearity has not yet been thoroughly investigated. Here, we demonstrate real-time observations of HNOy/NOy- as well as NOx production in a surface dielectric barrier discharge reactor containing distilled water. Synchronized two optical absorption spectroscopy systems were employed to simultaneously measure gas-phase NOx and liquid-phase HNOy/NOy- in the plasma reactor operated under different oxygen contents of 5, 20, and 50%. Our results showed that reducing the oxygen content in the reactor accelerated the chemical transition from O3 and NO3 to NO1,2, leading to a predominance of nitrite in PTW. Specifically, the NO3-rich period was extended with increasing O2 content, resulting in the production of nitrate-dominant PTW at low pH levels. Our findings highlight the potential for the selective generation of HNOy/NOy- in PTW through the active and passive control of NOx in a plasma reactor. The direct, real-time observation of NOx-HNOy/NOy- conversion presented here has potential for improving the control and optimization of PTW, thereby enhancing its applicability.

Evidence of direct interaction between cisplatin and the caspase-cleaved prostate apoptosis response-4 tumor suppressor.

Prostate apoptosis response-4 (Par-4) tumor suppressor protein has gained attention as a potential therapeutic target owing to its unique ability to selectively induce apoptosis in cancer cells, sensitize them to chemotherapy and radiotherapy, and mitigate drug resistance. It has recently been reported that Par-4 interacts synergistically with cisplatin, a widely used anticancer drug. However, the mechanistic details underlying this relationship remain elusive. In this investigation, we employed an array of biophysical techniques, including circular dichroism spectroscopy, dynamic light scattering, and UV-vis absorption spectroscopy, to characterize the interaction between the active caspase-cleaved Par-4 (cl-Par-4) fragment and cisplatin. Additionally, elemental analysis was conducted to quantitatively assess the binding of cisplatin to the protein, utilizing inductively coupled plasma-optical emission spectroscopy and atomic absorption spectroscopy. Our findings provide evidence of direct interaction between cl-Par-4 and cisplatin, and reveal a binding stoichiometry of 1:1. This result provides insights that could be useful in enhancing the efficacy of cisplatin-based and tumor suppressor-based cancer therapies.

Spectroscopic determination of the role of vanadyl oxygen in room temperature NH3 sensing by V2O5 nanoparticles.

In the present study, a multi-modal approach consisting of in-situ photoluminescence, Raman, and UV-Vis absorption spectroscopic studies is carried out along with chemiresistive sensing to unveil the mechanism of NH3 gas sensing by V2O5 nanoparticles in ambient air. V2O5 nanoparticles with an average size of 49 nm show a superior sensor response of 17 ± 1.5 % towards 1 ppm of NH3 gas with a response and recovery time of 96 s and 45 s, respectively. The photoluminescence and UV-Vis absorption studies in the presence of NH3 reveal electron doping to a new energy level at 1.84 eV, resulting in conduction band filling and increase in the optical band gap. The intensity of the photoluminescence spectrum shows an increase in the presence of NH3 gas as a result of this electron doping. The sensor response from the optical sensing carried out by in-situ photoluminescence study is 43 % for 40 ppm of NH3 gas. The vanadyl oxygen site is the most active in the sensing process, as evident by a selective enhancement in the intensity of V-O (vanadyl) bond vibration. This study gives an experimental evidence for the changes in optical and electronic properties of V2O5 on the adsorption of NH3 gas molecules.

Theoretical investigation complexation characteristics and UV-Vis absorption spectral properties of CdTe QDs with four capping agents.

In this paper, density functional theory (DFT) and time-dependent density functional theory (TDDFT) are used to study the complexation characteristics CdTe QDs with four different capping agents, i.e. 3-mercaptopropionic acid (MPA), reduced glutathione (GSH), 1-thioglycerol (TG) and 2-mercaptoethanesulfonate (MES). The properties of these complexes are analyzed by the complexation free energies, bond lengths, LOL, ADCH charges, frontier molecular orbitals and the UV-Vis absorption spectra. The results indicate that the four capping agents could form stable complexes with CdTe QDs. Whether the four capping agents interact with (CdTe)6 or (CdTe)9, MES has the strongest complexation ability with CdTe QDs and the MES-complexes are the most stable. For (CdTe)6, A2-MES is the most stable configuration. The complexation free energy and bond length of A2-MES are - 74.50 kcal/mol and 2.461 Å, respectively. When (CdTe)9 as substrate, A4-MES is the most stable configuration and corresponding complexation free energy is - 100.97 kcal/mol, which is followed by A4-MPA (- 57.75 kcal/mol) and A3-TG (- 60.20 kcal/mol), while A4-GSH (- 44.47 kcal/mol) is the weakest. Moreover, the electron amount transferred from MES to CdTe QDs is the most, and the ADCH charge value is 1.47 e. The absorption intensity of UV-visible light after complexation is also the largest. This is consistent with the result of the complexation free energy. Thus, it can be seen that the complexation abilities of four capping agents are in order of MES > MPA≈TG > GSH.

Target Prediction of 5,10,15,20-Tetrakis(4'-Sulfonatophenyl)-Porphyrin Using Molecular Docking.

Photodynamic therapy has the potential to be a new and effective cancer treatment. Even if in vitro and in vivo research show promise, the molecular mechanism remains unclear. In this study, molecular docking simulations predict the binding affinity of the 5,10,15,20-tetrakis(4'-sulfonatophenyl)-porphyrin tetraammonium photosensitizer on several potential targets in photodynamic treatment. Our results indicate that this photosensitizer binds to several receptor targets, including B-cell lymphoma 2 (BCL-2) and other related proteins BCL-xL, MCL-1, or A1. The binding affinity of the porphyrin derivative with human serum albumin was determined using UV-vis absorption spectroscopy and predicted using molecular docking. We conclude that the studied porphyrin photosensitizer binds to human serum albumin and may inhibit the cancer cell line through its interactions with HIS and MET AA residues from BCL-2, MCL-1, and ß-catenin receptors or through its low estimated free energy of binding when interacting with A1 and BCL-B receptors.

Asymmetric Phenyl Substitution: An Effective Strategy to Enhance the Photosensitizing Potential of Curcuminoids.

Curcumin has been demonstrated to exhibit photosensitized bactericidal activity. However, the full exploitation of curcumin as a photo-pharmaceutical active principle is hindered by fast deactivation of the excited state through the transfer of the enol proton to the keto oxygen. Introducing an asymmetry in the molecular structure through acting on the phenyl substituents is expected to be a valuable strategy to impair this undesired de-excitation mechanism competing with the therapeutically relevant ones. In this study, two asymmetric curcumin analogs were synthesized and characterized as to their electronic-state transition spectroscopic properties. Fluorescence decay distributions were also reconstructed. Their analysis confirmed the substantial stabilization of the fluorescent state with respect to the parent compound. Nuclear magnetic resonance experiments were performed with the aim of determining the structural features of the keto-enol ring and the strength of the keto-enol hydrogen bond. Electronic structure calculations were also undertaken to elucidate the effects of substitution on the features of the keto-enol semi-aromatic system and the proneness to proton transfer. Finally, their singlet oxygen-generation efficiency was compared to that of curcumin through the 9,10-dimethylanthracene fluorescent assay.

4-Nitrophenol-Loaded Magnetic Mesoporous Silica Hybrid Materials for Spectrometric Aptasensing of Carcinoembryonic Antigen.

Aptamer- or antibody-based sensing protocols have been reported for detecting carcinoembryonic antigen (CEA), but most exhibit complicated procedures or multiple reactions. In this work, we developed a one-step aptasensing protocol for the spectrometric determination of CEA based on 4-nitrophenol (4-NP)-loaded magnetic mesoporous silica nanohybrids (MMSNs) for bioresponsive controlled-release applications. To fabricate such a responsive-controlled sensing system, single-stranded complementary oligonucleotides relative to the CEA-specific aptamer were first modified on the aminated MMSN. Thereafter, 4-NP molecules blocked the pores with the assistance of the aptamers via a hybridization reaction. The introduced target CEA specifically reacted with the hybridized aptamer, thus detaching from the MMSN to open the gate. The loaded 4-NP molecules were released from the pores, as determined using ultraviolet-visible (UV-vis) absorption spectroscopy after magnetic separation. Under optimum conditions, the absorbance increased with an increase in the target CEA in the sample and exhibited a good linear relationship within the dynamic range of 0.1-100 ng mL-1, with a detection limit of 46 pg mL-1. Moreover, this system also displayed high specificity, good reproducibility, and acceptable accuracy for analyzing human serum specimens, in comparison with a commercialized human CEA-enzyme-linked immunosorbent assay (ELISA) kit.

Optical aptasensor based on silver nanoparticles for the colorimetric detection of adenosine.

A new and straightforward optical sensor for the colorimetric determination of adenosine (AD) in human urine samples was developed. The sensor comprised silver nanoparticles (AgNPs) as colorimetric elements and anti-AD aptamer (AP) as a recognition probe. In a solution containing AD and high concentration of NaCl, due to the unique binding of AD with AP, the aggregated metal nanomaterials dispersed in the solution, and the color intensity of the solution was changed accordingly. The absorbance of the solution was monitored for AD quantification. The method was applicable for the determination of AD in the concentration range of 60-280 nM with the detection limit of 21 nM. The relative standard deviation ranged from 4.8 to 8.8% for six replicates. The method showed excellent selectivity toward AD checked over some probable interfering compounds. To investigate the performance of AgNPs, the analytical characteristics of the method including linear range, detection limit, selectivity, and precision were compared with those obtained by a common AuNPs-based aptasensor. The reliability of the method was further ascertained for the detection of AD in urine samples of two lung cancer patients with percentage recoveries in the range of 98-107%.