Hidden Dissipation and Irreversibility in Maxwell’s Demon

Maxwell’s demon is an entity in a 150-year-old thought experiment that paradoxically appears to violate the second law of thermodynamics by reducing entropy without doing work. It has increasingly practical implications as advances in nanomachinery produce devices that push the thermodynamic limits imposed by the second law. A well-known explanation claiming that information erasure restores second law compliance fails to resolve the paradox because it assumes the second law a priori, and does not predict irreversibility. Instead, a purely mechanical resolution that does not require information theory is presented. The transport fluxes of mass, momentum, and energy involved in the demon’s operation are analyzed and show that they imply “hidden” external work and dissipation. Computing the dissipation leads to a new lower bound on entropy production by the demon. It is strictly positive in all nontrivial cases, providing a more stringent limit than the second law and implying intrinsic thermodynamic irreversibility. The thermodynamic irreversibility is linked with mechanical irreversibility resulting from the spatial asymmetry of the demon’s speed selection criteria, indicating one mechanism by which macroscopic irreversibility may emerge from microscopic dynamics.     

Effect of Natural Deep Eutectic Solvents on trans-Resveratrol Photo-Chemical Induced Isomerization and 2,4,6-Trihydroxyphenanthrene Electro-Cyclic Formation

trans-Resveratrol is a natural bioactive compound with well-recognized health promoting effects. When exposed to UV light, this compound can undergo a photochemically induced trans/cis isomerization and a 6π electrochemical cyclization with the subsequent formation of 2,4,6-trihydroxyphenanthrene (THP). THP is a potentially harmful compound which can exert genotoxic effects. In this work we improved the chromatographic separation and determination of the two resveratrol isomers and of THP by using a non-commercial pentafluorophenyl stationary phase. We assessed the effect of natural deep eutectic solvents (NaDES) as possible photo-protective agents by evaluating cis-resveratrol isomer and THP formation under different UV-light exposure conditions with the aim of enhancing resveratrol photostability and inhibiting THP production. Our results demonstrate a marked photoprotective effect exerted by glycerol-containing NaDES, and in particular by proline/glycerol NaDES, which exerts a strong inhibitory effect on the photochemical isomerization of resveratrol and significantly limits the formation of the toxic derivative THP. Considering the presence of resveratrol in various commercial products, these results are of note in view of the potential genotoxic risk associated with its photochemical degradation products and in view of the need for the development of green, eco-sustainable and biocompatible resveratrol photo-stable formulations.     

Structure Elucidation of Triterpenoid Saponins Found in an Immunoadjuvant Preparation of Quillaja brasiliensis Using Mass Spectrometry and 1H and 13C NMR Spectroscopy

An immunoadjuvant preparation (named Fraction B) was obtained from the aqueous extract of Quillaja brasiliensis leaves, and further fractionated by consecutive separations with silica flash MPLC and reverse phase HPLC. Two compounds were isolated, and their structures elucidated using a combination of NMR spectroscopy and mass spectrometry. One of these compounds is a previously undescribed triterpene saponin (Qb1), which is an isomer of QS-21, the unique adjuvant saponin employed in human vaccines. The other compound is a triterpene saponin previously isolated from Quillaja saponaria bark, known as S13. The structure of Qb1 consists of a quillaic acid residue substituted with a β-d-Galp-(1→2)-[β-d-Xylp-(1→3)]-β-d-GlcpA trisaccharide at C3, and a β-d-Xylp-(1→4)-α-l-Rhap-(1→2)-[α-l-Arap-(1→3)]-β-d-Fucp moiety at C28. The oligosaccharide at C28 was further substituted at O4 of the fucosyl residue with an acyl group capped with a β-d-Xylp residue.     

Thermal stability and energy of deactivation of free and immobilized amyloglucosidase in the saccharification of liquefied cassava starch

Amyloglucosidase from Novo (Copenhagen, Denmark) was immobilized in controlled pore silica particles with the silane-glutaraldehyde covalent method. Thermal stability of the free and immobilized enzyme (IE) was determined with 30% (w/v) α-amylase liquefied cassava starch, pH 4.5, temperatures from 35 to 75°C. Free amyloglucosidase maintained its activity practically constant for 240 min and temperatures up to 50°C. The IE has shown higher stability retaining its activity for the same period up to 60°C. Half-life for free enzyme was 20.6, 6.44, 2.07, 0.69, and 0.24 h for 55, 60, 65, 70, and 75°C, respectively, whereas the IE at the same temperatures had half-lives of 116.4, 30.88, 8.52, 2.44, and 0.73 h. The energy of thermal deactivation was thus 50.6 and 57.6 kcal/mol, respectively for the free and IE, confirming stabilization by immobilization.     

Distinguishing between Decaffeinated and Regular Coffee by HS-SPME-GC×GC-TOFMS,Chemometrics, and Machine Learning

Coffee, one of the most popular beverages in the world, attracts consumers by its rich aroma and the stimulating effect of caffeine. Increasing consumers prefer decaffeinated coffee to regular coffee due to health concerns. There are some main decaffeination methods commonly used by commercial coffee producers for decades. However, a certain amount of the aroma precursors can be removed together with caffeine, which could cause a thin taste of decaffeinated coffee. To understand the difference between regular and decaffeinated coffee from the volatile composition point of view, headspace solid-phase microextraction two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME-GC×GC-TOFMS) was employed to examine the headspace volatiles of eight pairs of regular and decaffeinated coffees in this study. Using the key aroma-related volatiles, decaffeinated coffee was significantly separated from regular coffee by principal component analysis (PCA). Using feature-selection tools (univariate analysis: t-test and multivariate analysis: partial least squares-discriminant analysis (PLS-DA)), a group of pyrazines was observed to be significantly different between regular coffee and decaffeinated coffee. Pyrazines were more enriched in the regular coffee, which was due to the reduction of sucrose during the decaffeination process. The reduction of pyrazines led to a lack of nutty, roasted, chocolate, earthy, and musty aroma in the decaffeinated coffee. For the non-targeted analysis, the random forest (RF) classification algorithm was used to select the most important features that could enable a distinct classification between the two coffee types. In total, 20 discriminatory features were identified. The results suggested that pyrazine-derived compounds were a strong marker for the regular coffee group whereas furan-derived compounds were a strong marker for the decaffeinated coffee samples.     

Analyses of intrinsic inhomogeneity and metal segregation in samples of Ag–Ge–Se glasses

Ge_ySe_(1−y) glasses are semiconductors but when Ag is added above certain threshold concentration, Ag_x[Ge_ySe_(1−y)]_(100−x) glasses behave as fast ionic conductors [Ureña et al., Solid State Ionics 176 (2005) 505]. This peculiar behavior may be attributed to the intrinsically inhomogeneous nature of these glasses where zones rich in metals coexist with zones of the host material. The conductivity transformation may be ascribed to the percolation of the Ag rich phase [Pradel et al., J. Phys.: Condens. Matter 15 (2003) S1561].Ag_x[Ge_0.25Se_0.75]_(100−x) glasses either massive or as films were obtained by melt quenching and pulsed laser deposition (PLD), respectively, in compositions belonging to the Se rich corner of the ternary phase diagram. Their amorphous nature and intermediate range order was checked employing X-ray diffractometry (XRD), the short range order was characterized by extended X-ray absorption fine structure (EXAFS) (Ge and Se K absorption edge) and their microstructure was characterized by scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS).     

Vibrational properties of superionic glasses (AgI)x(Ag2O nB2O3)1-x

In this letter we refer on the Raman-scattering measurements in superionic glasses (AgI)_x(Ag₂O nB₂O₃)_1-x where 0 ? x ? 0.5. The behaviour of the low-frequency Raman spectra, Δν < 250 cm^?1, has been interpreted as due to a vibrational density of states mainly due to the silver halide. Nonlinear increase of the Raman efficiency with the increase of AgI concentration has been found: a phenomenological explanation is presented.     

New source of dense, cryogenic positron plasmas

We have developed a new method, based on the ballistic transfer of preaccumulated plasmas, to obtain large and dense positron plasmas in a cryogenic environment. The method involves transferring plasmas emanating from a region with a low magnetic field (0.14 T) and relatively high pressure (10(-9) mbar) into a 15 K Penning-Malmberg trap immersed in a 3 T magnetic field with a base pressure better than 10(-13) mbar. The achieved positron accumulation rate in the high field cryogenic trap is more than one and a half orders of magnitude higher than the previous most efficient UHV compatible scheme. Subsequent stacking resulted in a plasma containing more than 1.2 x 10(9) positrons, which is a factor 4 higher than previously reported. Using a rotating wall electric field, plasmas containing about 20 x 10(6) positrons were compressed to a density of 2.6 x 10(10) cm(-3). This is a factor of 6 improvement over earlier measurements.