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The sensitivity to angular rotation of the top class Sagnac gyroscope GINGERINO is carefully investigated with standard statistical means, using 103 days of continuous operation and the available geodesic measurements of the Earth angular rotation rate. All features of the Earth rotation rate are correctly reproduced. The unprecedented sensitivity of fractions of frad/s is attained for long term runs. This excellent sensitivity and stability put Sagnac gyroscopes at the forefront for fundamental physics, in particular for tests of general relativity and Lorentz violation, where the sensitivity plays the key role to provide reliable data for deeper theoretical investigations. [ABSTRACT FROM AUTHOR]

RATIONALE The aim of this study was to demonstrate, and to characterize by high-resolution mass spectrometry that it is possible to preferentially induce covalent cross-links in peptides by using high-energy femtosecond ultraviolet (UV) laser pulses. The cross-link is readily formed only when aromatic amino acids are present in the peptide sequence. METHODS Three peptides, xenopsin, angiotensin I, and interleukin, individually or in combination, were exposed to high-energy femtosecond UV laser pulses, either alone or in the presence of spin trapping molecules, the reaction products being characterized by high resolution mass spectrometry. RESULTS High-resolution mass spectrometry and spin trapping strategies showed that cross-linking occurs readily, proceeds via a radical mechanism, and is the highly dominant reaction, proceeding without causing significant photo-damage in the investigated range of experimental parameters. CONCLUSIONS High-energy femtosecond UV laser pulses can be used to induce covalent cross-links between aromatic amino acids in peptides, overcoming photo-oxidation processes, that predominate as the mean laser pulse intensity approaches illumination conditions achievable with conventional UV light sources. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

A new algorithm for the Maximum Entropy Method (MEM) is proposed for recovering the lifetime distribution in time-resolved fluorescence decays. The procedure is based on seeking the distribution that maximizes the Skilling entropy function subjected to the chi-squared constraint χ ~ 1 through iterative linear approximations, LU decomposition of the Hessian matrix of the lagrangian problem and the Golden Section Search for backtracking. The accuracy of this algorithm has been investigated through comparisons with simulated fluorescence decays both of narrow and broad lifetime distributions. The proposed approach is capable to analyse datasets of up to 4,096 points with a discretization ranging from 100 to 1,000 lifetimes. A good agreement with non linear fitting estimates has been observed when the method has been applied to multi-exponential decays. Remarkable results have been also obtained for the broad lifetime distributions where the position is recovered with high accuracy and the distribution width is estimated within 3 %. These results indicate that the procedure proposed generates MEM lifetime distributions that can be used to quantify the real heterogeneity of lifetimes in a sample. [ABSTRACT FROM AUTHOR]

The photophysics of free base hemiporphyrazine has been studied by steady-state fluorescence and theoretical computations. The fluorescence spectrum shows two bands peaked at 420 and 675 nm, which, with the aid of theoretical computations, have been assigned to the emissions of two tautomers, differing for the position of the two central protons. [Copyright &y& Elsevier]

A Correction to this paper has been published: https://doi.org/10.1140/epjc/s10052-021-09199-1 [ABSTRACT FROM AUTHOR]

The pursuit of environmentally friendly solvents has become an essential research topic in sustainable chemistry and nanomaterial science. With the need to substitute toxic solvents in nanofabrication processes becoming more pressing, the search for alternative solvents has taken on a crucial role in this field. Additionally, the use of toxic, non-economical organic solvents, such as N-methyl-2 pyrrolidone and dimethylformamide, is not suitable for all biomedical applications, even though these solvents are often considered as the best exfoliating agents for nanomaterial fabrication. In this context, the success of producing two-dimensional transition metal dichalcogenides (2D TMDs), such as MoS2 and WS2, with excellent captivating properties is due to the ease of synthesis based on environment-friendly, benign methods with fewer toxic chemicals involved. Herein, we report for the first time on the use of cyrene as an exfoliating agent to fabricate monolayer and few-layered 2D TMDs with a versatile, less time-consuming liquid-phase exfoliation technique. This bio-derived, aprotic, green and eco-friendly solvent produced a stable, surfactant-free, concentrated 2D TMD dispersion with very interesting features, as characterized by UV–visible and Raman spectroscopies. The surface charge and morphology of the fabricated nanoflakes were analyzed using ς-potential and scanning electron microscopy. The study demonstrates that cyrene is a promising green solvent for the exfoliation of 2D TMD nanosheets with potential advantages over traditional organic solvents. The ability to produce smaller-sized—especially in the case of WS2 as compared to MoS2—and mono/few-layered nanostructures with higher negative surface charge values makes cyrene a promising candidate for various biomedical and electronic applications. Overall, the study contributes to the development of sustainable and environmentally friendly methods for the production of 2D nanomaterials for various applications. [ABSTRACT FROM AUTHOR]

The use of a cylindrical lens in femtosecond laser surface structuring is receiving attention to improve the processing efficiency. Here, we investigate the structures produced on a copper target, in air, by exploiting both spherical and cylindrical lenses for beam focusing, aiming at elucidating similarities and differences of the two approaches. The morphological features of the surface structures generated by ≈180 fs laser pulses at 1030 nm over areas of 8 × 8 mm2 were analyzed. For the spherical lens, micron-sized parallel channels are formed on the target surface, which is covered by subwavelength ripples and nanoparticles. Instead, the cylindrical lens leads to a surface decorated with ripples and nanoparticles with a negligible presence of micro-channels. Moreover, the morphological features achieved by focusing ≈180 fs laser pulses at 515 nm with the cylindrical lens and varying the scanning parameters were also studied. The experimental results evidence a direct effect of the hatch distance used in the scanning process on the target surface that contains dark and bright bands corresponding to regions where the rippled surface contains a richer decoration or a negligible redeposition of nanoparticles. Our findings can be of interest in large area surface structuring for the selection of the more appropriate focusing configuration according to the final application of the structured surface. [ABSTRACT FROM AUTHOR]

The interaction between two-dimensional nanoflakes and bacteria in water-based physiological liquids is a hot topic that unveils new types of phenomena and is fundamental to bioscience applications. In this work, we extend Derjaguin, Landau, Verwey, and Overbeek theory (DLVO theory) that describes the properties of nano-objects in solutions, to the case of two-dimensional nanoflakes interacting with bacteria cell membranes, both for Gram-positive and Gram-negative bacteria. We have studied the role of the bacterial shape, membrane potential, and two-dimensional nanomaterials nature showing the interplay of these parameters in determining whether the interactions are attractive or repulsive and whether electrostatic or van der Waals forces are dominant. We calculated the interaction distances at equilibrium for different bacterial species and hydrophobic nanomaterials such as M o S 2 in two environmentally friendly solvents, water and cyrene. [ABSTRACT FROM AUTHOR]

The article discusses various reports published within the issue, including one on non-sequential double ionisation of atoms, another on the optimal waveform for an efficient energy transfer from the electromagnetic field to the electron liberated into ionisation and another on the coherent optical and acoustic oscillations.

• The new reported compounds easily switch from the trans to the cis form after LED irradiation. • The UV spectra reveal the reversibility of trans↔cis isomerisation and the cis isomers are detectable in 1H NMR spectra. • Kinetics of the trans↔cis isomerisations were evaluated by UV and fast UV experiments. • The compounds differently affect the dynamic of MT polymerization after UV irradiation. • Under irradiation the compounds affect HCT-116 p53-/- cell viability. In order to expand the class of diazocompounds able to act as photo-activable microtubule inhibitors the potential of azo-heteroarenes has been explored. In this paper we focus on the synthesis, physical properties and biological effects of methyl rac -2-(2-((E)-(4-((R)-2,3-dihydroxypropoxy)phenyl) diazenyl)-1H-pyrrol-1- yl)-3-hydroxypropanoate (1a) and methyl rac -2-(2-((E)-(4-((S)-2,3-dihydroxypropoxy)phenyl) diazenyl)-1H-pyrrol-1- yl)-3-hydroxypropanoate (1b). Preliminary biological studies on the HCT-116 p53-/- cancer cell line have shown that the weak antiproliferative action of the trans isomers of these molecules, especially of 1a, is enhanced upon LED light irradiation at 435 nm. On A375 cells the molecules have not shown any effect on cell viability either in the dark or under irradiation. Moreover, the two diastereomeric components of 1a as pure stereomers have been synthesized and characterized for their chemical-physical properties. Interestingly, upon irradiation, 1a has shown an antiproliferative activity on the HCT-116 p53-/- cells greater than that of the pure stereomers, 1 RR and 1 RS. Tubulin polymerization assay has also demonstrated that 1a , 1RR and 1RS inhibit tubulin aggregation mostly after exposure of the samples to LED light irradiation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Laser surface structuring of copper for secondary electron emission reduction. • Femtosecond laser processing at different ambiences for 515 and 1030 nm. • Irradiation in air with 515 nm found to be the best for proposed application. • Impact of LIPSS on the copper surface resistance does not appear to be critical for present accelerators. • Laser surface processing to enhance performances of future particle accelerators. One of the main limitations for future high-performance accelerators operating with positively charged particles is the formation of an electron-cloud inside the beam vacuum chamber, giving rise to instabilities. The Secondary Electron Yield (SEY) of the beam-facing surfaces gives a measure of the mechanism which drives this phenomenon. The laser-induced periodic structure formation on Cu surfaces has been demonstrated as a promising process to reduce SEY. In view of applications in beam chambers, we studied the laser process influence on SEY for 515 and 1030 nm wavelength femtosecond pulses on copper in different ambiences (air, nitrogen, vacuum). Depending on used process conditions, the surface composition differs, structures with varying aspect ratio are formed, i.e., periodic ripples and large-scale channels. Treatment in air at 515 nm is the most efficient for the formation of deeper structures allowing SEY maximum reduction first down to 1.6–1.7 and then below unity upon electron irradiation, thereby totally suppressing electron-cloud. Increasing the laser fluence, SEY will further reduce due to surface roughness enhancement via nanoparticle redeposition. This study reveals the fundamental role of LIPSS treatments to enable surface treatment in large-scale accelerator installations, where particle-free components are desired, and paves the way to potential future applications. [ABSTRACT FROM AUTHOR]

The identification of protein-protein interaction networks in living cells is becoming increasingly fundamental to elucidate main biological processes and to understand disease molecular bases on a system-wide level. We recently described a method ( LUCK , L aser U V C ross-lin K ing) to cross-link interacting protein surfaces in living cells by UV laser irradiation. By using this innovative methodology, that does not require any protein modification or cell engineering, here we demonstrate that, upon UV laser irradiation of HeLa cells, a direct interaction between GAPDH and alpha-enolase was “frozen” by a cross-linking event. We validated the occurrence of this direct interaction by co-immunoprecipitation and Immuno-FRET analyses. This represents a proof of principle of the LUCK capability to reveal direct protein interactions in their physiological environment. [ABSTRACT FROM AUTHOR]

Background: Biosensor-based detection provides a rapid and low-cost alternative to conventional analytical methods for revealing the presence of the contaminants in water as well as solid matrices. Although important to be detected, small analytes (few hundreds of Daltons) are an issue in biosensing since the signal they induce in the transducer, and specifically in a Quartz-Crystal Microbalance, is undetectable. A pesticide like parathion (M = 292 Da) is a typical example of contaminant for which a signal amplification procedure is desirable. Methods/Findings: The ballasting of the analyte by gold nanoparticles has been already applied to heavy target as proteins or bacteria to improve the limit of detection. In this paper, we extend the application of such a method to small analytes by showing that once the working surface of a Quartz-Crystal Microbalance (QCM) has been properly functionalized, a limit of detection lower than 1 ppb is reached for parathion. The effective surface functionalization is achieved by immobilizing antibodies upright oriented on the QCM gold surface by a simple photochemical technique (Photonic Immobilization Technique, PIT) based on the UV irradiation of the antibodies, whereas a simple protocol provided by the manufacturer is applied to functionalize the gold nanoparticles. Thus, in a non-competitive approach, the small analyte is made detectable by weighing it down through a “sandwich protocol” with a second antibody tethered to heavy gold nanoparticles. The immunosensor has been proved to be effective against the parathion while showing no cross reaction when a mixture of compounds very similar to parathion is analyzed. Conclusion/Significance: The immunosensor described in this paper can be easily applied to any small molecule for which polyclonal antibodies are available since both the functionalization procedure of the QCM probe surface and gold nanoparticle can be applied to any IgG, thereby making our device of general application in terms of target analyte. [ABSTRACT FROM AUTHOR]

A hallmark to decipher bioprocesses is to characterize protein-protein interactions in living cells. To do this, the development of innovative methodologies, which do not alter proteins and their natural environment, is particularly needed. Here, we report a method (LUCK, Laser UV Cross-linKing) to in vivo cross-link proteins by UV-laser irradiation of living cells. Upon irradiation of HeLa cells under controlled conditions, cross-linked products of glyceraldehyde-3-phosphate dehydrogenase (GAPDH) were detected, whose yield was found to be a linear function of the total irradiation energy. We demonstrated that stable dimers of GAPDH were formed through intersubunit cross-linking, as also observed when the pure protein was irradiated by UV-laser in vitro. We proposed a defined patch of aromatic residues located at the enzyme subunit interface as the cross-linking sites involved in dimer formation. Hence, by this technique, UV-laser is able to photofix protein surfaces that come in direct contact. Due to the ultra-short time scale of UV-laser-induced cross-linking, this technique could be extended to weld even transient protein interactions in their native context. [ABSTRACT FROM AUTHOR]

Oriented antibodies are tethered on the gold surface of a quartz crystal microbalance through the photonics immobilization technique so that limit of detection as low as 50 nM and 140 nM are achieved for parathion and patulin, respectively. To make these small analytes detectable by the microbalance, they have been weighed down through a “sandwich protocol” with a second antibody. The specificity against the parathion has been tested by checking the immunosensor response to a mixture of compounds similar to parathion, whereas the specificity against the patulin has been tested with a real sample from apple puree. In both cases, the results are more than satisfactory suggesting interesting outlook for the proposed device. [ABSTRACT FROM AUTHOR]

Thephotophysical and photochemical properties of 5-benzyluraciland 5,6-benzyluracil, the latter produced by photocyclization of theformer through irradiation with femtosecond UV laser pulses, are investigatedboth experimentally and theoretically. The absorption spectra of thetwo molecules are compared, and the principal electronic transitionsinvolved are discussed, with particular emphasis on the perturbationinduced on the two chromophore species (uracil and benzene) by theirproximity. The photoproduct formation for different irradiation timeswas verified with high-performance liquid chromatography and nuclearmagnetic resonance measurements. The steady-state fluorescence demonstratesthat the fluorescence is a distinctive physical observable for detectionand selective identification of 5- and 5,6-benzyluracil. The principalelectronic decay paths of the two molecules, obtained through TDDFTcalculations, explain the features observed in the emission spectraand the photoreactivity of 5-benzyluracil. The order of magnitudeof the lifetime of the excited states is derived with steady-statefluorescence anisotropy measurements and rationalized with the helpof the computational findings. Finally, the spectroscopic data collectedare used to derive the photocyclization and fluorescence quantum yields.In obtaining a global picture of the photophysical and photochemicalproperties of the two molecules, our findings demonstrates that theuse of 5-benzyluracil as a model system to study the proximity relationsof a DNA base with a close-lying aromatic amino acid is valid at alocal level since the main characteristics of the decay processesfrom the excited states of the uracil/thymine molecules remain almostunchanged in 5-benzyluracil, the main perturbation arising from thepresence of the close-lying aromatic group. [ABSTRACT FROM AUTHOR]

Photonic immobilization technique (PIT) has been used to develop an immunosensor for the detection of parathion. An antibody solution has been activated by breaking the disulfide bridge in the triad Trp/Cys-Cys through absorption of ultrashort UV laser pulses. The free thiol groups so produced interact with gold lamina making the antibody oriented upside, that is, with its variable parts exposed to the environment, thereby greatly increasing the detection efficiency. PIT has been applied to anchor polyclonal antiparathion antibodies to the gold electrode of a Quartz Crystal Microbalance (QCM) giving rise to very high detection sensitivity once the parathion is made heavier by complexion with BSA (bovine serum albumin), this latter step only required by the mass based transducer used in this case. The comparison of the sensor response with irradiated antibodies against different analytes shows that the high degree of antibody specificity is not affected by PIT nor is it by the complexion of parathion with BSA. These results pave the way to important applications in biosensing, since the widespread occurrence of the Trp/Cys-Cys residues triads in proteins make our procedure very general and effective to detect light analytes. [ABSTRACT FROM AUTHOR]

A monolithic silica gel matrix with entrapped glucose oxidase (GOD) was constructed as a bioactive element in an optical biosensor for glucose determination. Intrinsic fluorescence of free and immobilised GOD was investigated in the visible range in presence of different glucose concentrations by time-resolved spectroscopy with time-correlated single-photon counting detector. A three-exponential model was used for analysing the fluorescence transients. Fractional intensities and mean lifetime were shown to be sensitive to the enzymatic reaction and were used for obtaining calibration curve for glucose concentration determination. The sensing system proposed achieved high resolution (up to 0:17 mM) glucose determination with a detection range from 0:4 mM to 5 mM. [ABSTRACT FROM AUTHOR]

The synthesis of two 5′-end (4-dimethylamino)azobenzene conjugated G-quadruplex forming aptamers, the thrombin binding aptamer (TBA) and the HIV-1 integrase aptamer (T30695), was performed. Their structural behavior was investigated by means of UV, CD, fluorescence spectroscopy, and gel electrophoresis techniques in K+-containing buffers and water-ethanol blends. Particularly, we observed that the presence of the 5′-(4-dimethylamino)azobenzene moiety leads TBA to form multimers instead of the typical monomolecular chair-like G-quadruplex and almost hampers T30695 G-quadruplex monomers to dimerize. Fluorescence studies evidenced that both the conjugated G-quadruplexes possess unique fluorescence features when excited at wavelengths corresponding to the UV absorption of the conjugated moiety. Furthermore, a preliminary investigation of the trans-cis conversion of the dye incorporated at the 5′-end of TBA and T30695 showed that, unlike the free dye, in K+-containing water-ethanol-triethylamine blend the trans-to-cis conversion was almost undetectable by means of a standard UV spectrophotometer. [ABSTRACT FROM AUTHOR]

The identification of molecules whose biological activity can be properly modulated by light is a promising therapeutic approach aimed to improve drug selectivity and efficacy on the molecular target and to limit the side effects compared to traditional drugs. Recently, two photo-switchable diastereomeric benzodiazopyrrole derivatives 1RR and 1RS have been reported as microtubules targeting agents (MTAs) on human colorectal carcinoma p53 null cell line (HCT 116 p53-/-). Their IC50 was enhanced upon Light Emitting Diode (LED) irradiation at 435 nm and was related to their cis form. Here we have investigated the photo-responsive behavior of the acid derivatives of 1RR and 1RS, namely, d1RR and d1RS, in phosphate buffer solutions at different pH. The comparison of the UV spectra, acquired before and after LED irradiation, indicated that the trans→cis conversion of d1RR and d1RS is affected by the degree of ionization. The apparent rate constants were calculated from the kinetic data by means of fast UV spectroscopy and the conformers of the putative ionic species present in solution (pH range: 5.7–8.0) were modelled. Taken together, our experimental and theoretical results suggest that the photo-conversions of transd1RR/d1RS into the corresponding cis forms and the thermal decay of cisd1RR/d1RS are dependent on the presence of diazonium form of d1RR/d1RS. Finally, a photo-reaction was detected only for d1RR after prolonged LED irradiation in acidic medium, and the resulting product was characterized by means of Liquid Chromatography coupled to High resolution Mass Spectrometry (LC-HRMS) and Nuclear Magnetic Resonance (NMR) spectroscopy. [ABSTRACT FROM AUTHOR]

Two dimensional materials beyond graphene such as MoS2 and WS2 are novel and interesting class of materials whose unique physico-chemical properties can be exploited in applications ranging from leading edge nanoelectronics to the frontiers between biomedicine and biotechnology. To unravel the potential of TMD crystals in biomedicine, control over their production through green and scalable routes in biocompatible solvents is critically important. Furthermore, considering multiple applications of eco-friendly 2D dispersions and their potential impact onto live matter, their toxicity and antimicrobial activity still remain an open issue. Herein, we focus on the current demands of 2D TMDs and produce high-quality, few-layered and defect-free MoS2 nanosheets, exfoliated and dispersed in pure water, stabilized up to three weeks. Hence, we studied the impact of this material on human cells by investigating its interactions with three cell lines: two tumoral, MCF7 (breast cancer) and U937 (leukemia), and one normal, HaCaT (epithelium). We observed novel and intriguing results, exhibiting evident cytotoxic effect induced in the tumor cell lines, absent in the normal cells in the tested conditions. The antibacterial action of MoS2 nanosheets is then investigated against a very dangerous gram negative bacterium, such as two types of Salmonellas: ATCC 14028 and wild-type Salmonella typhimurium. Additionally, concentration and layer-dependent modulation of cytotoxic effect is found both on human cells and Salmonellas. [ABSTRACT FROM AUTHOR]