A rotational spectroscopy study of microsolvation effects on intramolecular proton transfer in trifluoroacetylacetone-(H2O)1-3.

Trifluoroacetylacetone (TFAA) has two enol forms, which can switch to each other via proton transfer. While much attention has been paid to their conformational preferences, the influence of microsolvation on regulating the proton position remains unexplored. Herein, we report the rotational spectra of trifluoroacetylacetone-(water)n (n = 1-3) investigated by chirped pulse Fourier transform microwave spectroscopy in the 2-8 GHz frequency range. Two conformers were identified for both TFAA-H2O and TFAA-(H2O)2, while only one conformer was characterized for TFAA-(H2O)3. The results indicate that water binding on the CH3 side stabilizes the enolF form, whereas water binding on the CF3 side stabilizes the enolH form. The enolF form predominates over the enolH form in these hydrated complexes, which contrasts with the fact that only enolH exists in isolated TFAA. EnolH becomes preferred only when water inserts itself into the intramolecular hydrogen bond. Instanton theory calculations reveal that the proton transfer reaction is dominated by quantum tunneling at low temperatures, leading to the stable existence of only one enol form in each configuration of the hydrated clusters.

Hyperfine-resolved spectra of HDS together with a global ro-vibrational analysis.

Despite their chemical simplicity, the spectroscopic investigation of light hydrides, such as hydrogen sulfide, is challenging due to strong hyperfine interactions and/or anomalous centrifugal-distortion effects. Several hydrides have already been detected in the interstellar medium, and the list includes H2S and some of its isotopologues. Astronomical observation of isotopic species and, in particular, those bearing deuterium is important to gain insights into the evolutionary stage of astronomical objects and to shed light on interstellar chemistry. These observations require a very accurate knowledge of the rotational spectrum, which is so far limited for mono-deuterated hydrogen sulfide, HDS. To fill this gap, high-level quantum-chemical calculations and sub-Doppler measurements have been combined for the investigation of the hyperfine structure of the rotational spectrum in the millimeter- and submillimeter-wave region. In addition to the determination of accurate hyperfine parameters, these new measurements together with the available literature data allowed us to extend the centrifugal analysis using a Watson-type Hamiltonian and a Hamiltonian-independent approach based on the Measured Active Ro-Vibrational Energy Levels (MARVEL) procedure. The present study thus permits to model the rotational spectrum of HDS from the microwave to far-infrared region with great accuracy, thereby accounting for the effect of the electric and magnetic interactions due to the deuterium and hydrogen nuclei.

Insights into the molecular structure and infrared spectrum of the prebiotic species aminoacetonitrile.

Aminoacetonitrile is an interstellar molecule with a prominent prebiotic role, already detected in the chemically-rich molecular cloud Sagittarius B2(N) and postulated to be present in the atmosphere of the largest Saturn's moon, Titan. To further support its observation in such remote environments and laboratory experiments aimed at improving our understanding of interstellar chemistry, we report a thorough spectroscopic and structural characterization of aminoacetonitrile. Equilibrium geometry, fundamental bands as well as spectroscopic and molecular parameters have been accurately computed by exploiting a composite scheme rooted in the coupled-cluster theory that accounts for the extrapolation to the complete basis set limit and core-correlation effects. In addition, a semi-experimental approach that combines ground-state rotational constants for different isotopic species and calculated vibrational corrections has been employed for the structure determination. From the experimental side, we report the analysis of the three strongest fundamental bands of aminoacetonitrile observed between 500 and 1000 cm-1 in high-resolution infrared spectra. More generally, all computed band positions are in excellent agreement with the present and previous experiments. The only exception is the ν15 band, for which we provide a revision of the experimental assignment, now in good agreement with theory.

Rotational Spectra of Unsaturated Carbon Chains Produced by Pyrolysis: The Case of Propadienone, Cyanovinylacetylene, and Allenylacetylene.

Several interstellar molecules are highly reactive unsaturated carbon chains, which are unstable under terrestrial conditions. Laboratory studies in support of their detection in space thus face the issue of how to produce these species and how to correctly model their rotational energy levels. In this work, we introduce a general approach for producing and investigating unsaturated carbon chains by means of selected test cases. We report a comprehensive theoretical/experimental spectroscopic characterization of three species, namely, propadienone, cyanovinylacetylene, and allenylacetylene, all of them being produced by means of flash vacuum pyrolysis of a suitable precursor. For each species, quantum-chemical calculations have been carried out with the aim of obtaining accurate predictions of the missing spectroscopic information required to guide spectral analysis and assignment. Rotational spectra of the title molecules have been investigated up to 400 GHz by using a frequency-modulation millimeter-/submillimeter-wave spectrometer, thus significantly extending spectral predictions over a wide range of frequency and quantum numbers. A comparison between our results and those available in the literature points out the clear need of the reported laboratory measurements at higher frequencies for setting up accurate line catalogs for astronomical searches.

Spectroscopic and Computational Characterization of 2-Aza-1,3-butadiene, a Molecule of Astrochemical Significance.

Being N-substituted unsaturated species, azabutadienes are molecules of potential relevance in astrochemistry, ranging from the interstellar medium to Titan's atmosphere. 2-Azabutadiene and butadiene share a similar conjugated π system, thus allowing investigation of the effects of heteroatom substitution. More interestingly, 2-azabutadiene can be used to proxy the abundance of interstellar butadiene. To enable future astronomical searches, the rotational spectrum of 2-azabutadiene has been investigated up to 330 GHz. The experimental work has been supported and guided by accurate computational characterization of the molecular structure, energetics, and spectroscopic properties of the two possible forms, trans and gauche. The trans species, more stable by about 7 kJ/mol than gauche-2-azabutadiene, has been experimentally observed, and its rotational and centrifugal distortion constants have been obtained with remarkable accuracy, while theoretical estimates of the spectroscopic parameters are reported for gauche-2-azabutadiene.

High Elongation and Transparent Nacre-Inspired PVA/MMT Nanocomposites.

Currently, high strength nacre-inspired PVA/MMT (polyvinyl alcohol/montmorillonite) nanocomposites with high MMT nanofiller content (50-70 wt%) have been constructed successfully. However, this seriously sacrifices the elongation and reduces the corresponding transparency. In this paper, high elongation and transparent PVA/MMT nanocomposites with high MMT content are prepared by the evaporation-induced assembly with the introduction of the micro-crosslinking. Results demonstrate that the micro-crosslinking can inhibit the formation of rod-shaped arrays, and contribute to a more ordered layered microstructure, where an elongation of 76.2% in 47.8 wt% MMT content nanocomposites is gained, nearly 19 times of that of non-crosslinked nanocomposites (ultimate strain is 4.1%). This provides a potential approach for compromise between high strength and excellent elongation at the same MMT content. Moreover, disappearance of rod-shaped arrays and resultant ordered layered microstructure make eventual films more transparent.

Investigations into the Role of Friction for Rigid Penetration into Concrete-Like Material Targets.

Currently, it appears that there is a lack of understanding related to the role of SSF, in the two-phase behavior of the deceleration history, which is an issue discussed recently in the impact dynamics field. This paper analytically and numerically focuses on the effect of SSF on the projectile deceleration characteristic of concrete-like targets. Firstly, the penetration process according to the two-phase feature of the projectile deceleration is revised, where analytical results indicate that the SSF has a phased feature corresponding to the two-phase behavior of the deceleration history. Furthermore, a series of numerical simulations are conducted to understand the role of SSF more clearly. Simulation results show a similar conclusion to the analyses of the two-phase penetration process; at the range below a certain critical striking velocity, adding friction can reproduce the experimental data; when exceeding the critical striking velocity, the simulated results without considering friction are closest to the experimental data. Hence, it could be gained that the role exchange between the SSF and the dynamic term contributes to the two-phase penetration behavior for concrete-like materials. This indicates that the sensitivity of SSF to the penetration process is one of the factors driving the two-phase feature.

Preparation of Aptamer Responsive DNA Functionalized Hydrogels for the Sensitive Detection of α-Fetoprotein Using SERS Method.

Hepatocellular carcinoma (HCC), which is one of the three major cancers, has attracted growing attention due to its high mortality, health care cost, and circumscribed therapeutic methods. Hence, the development of a fast, accurate, and flexible method to detect α-fetoprotein (AFP), the specific marker of HCC, is significant for diagnosis and treatment of cancer. Here, we constructed a novel SERS biosensing platform combining the target-responsive DNA hydrogel for the sensitive detection of AFP. The linker strand in DNA hydrogel is an aptamer that can specifically recognize AFP and accurately control the release of immunoglobulin G (IgG) encapsulated in hydrogel. In the presence of AFP, the hydrogels were disentangled and the IgG was released. Thereafter, the released IgG was captured by SERS probes and biofunctional magnetic beads through formation of sandwich-like structures, resulting in the signal of Raman tags decreasing in the supernatant after magnetic separation. Due to the ultrahigh sensitivity of the SERS biosensor, the proposed method has a wide detection linear range (50 pg/mL to 0.5 µg/mL) and a detection limit down to 50 pg/mL. Moreover, the sequence of the linker strand in the DNA hydrogel can be specifically encoded into a new aptamer that responds to other cancer markers. This convenient and inexpensive detection method provides a new strategy for the detection of tumor markers.

Structural rearrangement of the acrylonitrile (AN) cluster in the gas phase under VUV one-photon radiation explored by mass-selected infrared spectroscopy.

Acrylonitrile (AN), one of the most abundant nitriles in space, is considered to closely relate to the formation of interstellar prebiotic nitrogen-containing aromatics. Herein, we measured the vibrational spectra of acrylonitrile cluster cations (AN)2,3+ in a supersonic jet using infrared (IR) dissociation with vacuum-ultraviolet (VUV) photoionization and time-of-flight mass spectroscopy. Interestingly, the observed IR spectra demonstrate that a new molecular ion [Formula: see text] , is generated from the dimer and trimer of AN upon VUV single-photo ionization. Calculation results reveal that the new molecular cations can be generated through a relative low energy barrier after ionization of the neutral (AN)2. However, the reaction pathways are barrierless for the trimer, in which the third solvent AN acts as a catalyst. The mechanisms of those reactions also have been discussed in detail. This study contributes to a deeper understanding of ion-molecule reaction in gas-phase and the quest for the formation of prebiotic N -containing molecules in the outer space.

Competitive aptasensor with gold nanoparticle dimers and magnetite nanoparticles for SERS-based determination of thrombin.

It is known that the intensity of surface-enhanced Raman scattering (SERS) of monomeric gold nanoparticles (GNPs) is insufficient for ultrasensitive analysis. The authors describe dimeric GNPs for use in a competitive SERS and aptamer based assay for thrombin. The reagent 1,2-bis(4-pyridyl) ethylene serves as both the coupling agent and the Raman reporter on the GNP dimers. In the presence of thrombin, the hybridization of two aptamers, one attached to the GNP dimers, the other to magnetic nanoparticles, is competitively prevented. This method takes advantage of the unique "hot spots" of the GNP dimers to amplify the Raman signal. This results in an ultra-sensitive thrombin assay when compared to assays using GNP monomers. The limit of detection is as low as 1 fM of thrombin. The Raman intensity, best measured at 1612 cm-1, increases linearly in the 1 fM to 10 nM thrombin concentration range. The method was applied to the determinaiton of thrombin in spiked simulated body fluid and human serum. Graphical abstract This method takes advantage of the unique "hot spots" of the gold nanoparticle dimers to amplify the Raman signal. The dimers are linked to the magnetic nanoparticles via an aptamer. The use of both competitive displacement and magnetic separation greatly improves the sensitivity of the thrombin assay.

Detection of microRNA using a polydopamine mediated bimetallic SERS substrate and a re-circulated enzymatic amplification system.

A surface-enhanced Raman scattering (SERS) method is described for the determination of microRNA that is associated with various forms of cancer. The substrate consists of functionalized gold-silver bimetallic structure, and the sensitivity is strongly enhanced by making use of a re-circulated enzymatic amplification system (REAS). Poly-dopamine acts as both a reductant and a protective of the substrates. It was employed to link the gold core and silver satellite. The unique "hot spots" consisting of a Au@PDA@Ag nanocomposite improve the Raman signal and sensitivity. The reductive feature of PDA can prevent the susceptible oxidation of metallic silver to maintain the high Raman activity. To improve the sensitivity of the assays, a re-circulated enzymatic amplification system was developed in which the nicking endonuclease triggers the nucleic acid reaction system to enter an amplified cycle. By integrating the bimetallic nanosubstrate and magnetic separation into the REAS, microRNA can be detected by SERS (best at the Raman band of 1586 cm-1) with a limit of detection as low as 0.2 fM. In our perception, the assay provides an exciting new avenue to study the expression of tumor genes. Thus, it holds vast promise in cancer diagnosis. Graphical abstract Schematic presentation of the SERS method based on poly-dopamine mediated bimetallic SERS substrate and re-circulated enzymatic amplification.

A novel SERS-based magnetic aptasensor for prostate specific antigen assay with high sensitivity.

The accurate and highly sensitive detection of prostate specific antigen (PSA) is particularly important, especially for obese men and patients. In this report, we present a novel aptamer-based surface-enhanced Raman scattering (SERS) sensor that employs magnetic nanoparticles (MNPs) core-Au nanoparticles (AuNPs) satellite assemblies to detect PSA. The high specific biorecognition between aptamer and PSA caused the dissolution of the core-satellite assemblies, thus the concentration of functionalized AuNPs (signal probes) existing in the supernatant was on the rise with the continual addition of PSA. The aptamer-modified MNPs were used as supporting materials and separation tools in the present sensor. With the assistance of magnet, the mixture was removed from the supernatant for the concentration effects. It was found that the corresponding SERS signals from the supernatant were in direct correlation to PSA concentrations over a wide range and the limit of detection (LOD) was as low as 5.0pg/mL. Excellent recovery was also obtained to assess the feasibility of this method for human serum samples detection. All of these results show a promising application of this method. And this novel sensor can be used for the accurate and highly sensitive detection of PSA in clinic samples in the future.

A novel SERS nanoprobe based on the use of core-shell nanoparticles with embedded reporter molecule to detect E. coli O157:H7 with high sensitivity.

The authors report on a surface-enhanced Raman scattering (SERS) nanoprobe for the specific detection of Escherichia coli O157:H7 (E. coli O157:H7). Gold nanoparticles (AuNPs) were coated with a thick silica shell, and the Raman reporter (4,4'-dipyridyl) was embedded between gold nanoparticle and silica shell. This technique prevents any external effects on the AuNPs from the environment and avoids any interaction between the Raman reporter and possible impurities. Compared to the SERS nanoprobe of the conventional AuNP/AgNP type, the present nanoprobe can be applied in complex biochemical circumstances without aggregation because of its excellent stability. The SERS nanoprobeis stable for up to 50 h. The probe was applied to the SERS detection of E. coli O157:H7 by exploiting the Raman band peaking at 1612 cm-1 of 4,4'-dipyridyl (DP). The limit of detection is as low as 10 CFU·mL-1. The technique was successfully employed to the detection of E. coli O157:H7 in real samples, achieving recoveries between 95.5 and 114.8%. Graphical abstract A novel surface-enhanced Raman scattering (SERS) nanoprobe based on the silica encapsulated gold nanoparticles (SEGNs) combining with the functionalized magnetic nanoparticles (MNPs), detecting E. coli O157:H7 with high sensitivity and specificity.