219 research outputs found
Partition function, metastability, and kinetics of the escape transition for an ideal chain
No full textThe exact partition of the gaussian chain squeezed between two cylinders for a phase transition in a single macromolecule is analyzed. The polymer chain is squeezed between two pistons which results in abrupt transition from a confined coil state to an inhomogeneous conformation. The landau free energy is used in a one dimensional fokker-plank equation to predict the life-time of the metastable states. The analysis shows that the mean first passage time is estimated on the basis of the fokker-planck formalism.Baumgartner W, 2000, P NATL ACAD SCI USA, V97, P4005, DOI 10.1073-pnas.070052697; Carslaw H, 1947, CONDUCTION HEAT SOLI; Chaikin P.M., 2000, PRINCIPLES CONDENSED; De Gennes PG, 1979, SCALING CONCEPTS POL; de Gennes P.-G., 1993, PHYS LIQUID CRYSTALS; DESCLOIZEAUX G, 1990, POLYM SOLUTION THEIR; Doi M, 1986, THEORY POLYM DYNAMIC; EISENRIEGLER E, 1982, J CHEM PHYS, V77, P6296, DOI 10.1063-1.443835; Eisenriegler E., 1998, LECT NOTES PHYS, V508; Ennis J, 1999, PHYS REV E, V60, P6906, DOI 10.1103-PhysRevE.60.6906; Fleer G. J., 1993, POLYM INTERFACES; Flory PJ, 1953, PRINCIPLES POLYM CHE; Grosberg AY, 1994, STAT PHYS MACROMOLEC; GUFFOND MC, 1997, LANGMUIR, V13, P1591; Haupt BJ, 1999, LANGMUIR, V15, P3886, DOI 10.1021-la981112v; Hugel T, 2001, MACROMOLECULES, V34, P1039, DOI 10.1021-ma0009404; Hugel T, 2001, MACROMOL RAPID COMM, V22, P989, DOI 10.1002-1521-3927(20010901)22:13989::AID-MARC9893.0.CO;2-D; Jimenez J, 1998, LANGMUIR, V14, P2598, DOI 10.1021-la971233f; Klushin LI, 2002, PHYS REV E, V66, DOI 10.1103-PhysRevE.66.036114; Landau L. D., 1976, STAT PHYS; Leermakers FAM, 2002, MACROMOLECULES, V35, P8640, DOI 10.1021-ma020718u; Milchev A, 1999, PHYS CHEM CHEM PHYS, V1, P2083, DOI 10.1039-a809795j; Milchev A, 1999, EUROPHYS LETT, V47, P675, DOI 10.1209-epl-i1999-00442-2; Muthukumar M, 2001, PHYS REV LETT, V86, P3188, DOI 10.1103-PhysRevLett.86.3188; Senden TJ, 2001, CURR OPIN COLLOID IN, V6, P95, DOI 10.1016-S1359-0294(01)00067-X; Sevick EM, 1999, MACROMOLECULES, V32, P6841, DOI 10.1021-ma990589q; Skvortsov AM, 2001, J CHEM PHYS, V115, P1586, DOI 10.1063-1.1374210; Skvortsov AM, 2000, J CHEM PHYS, V112, P7238, DOI 10.1063-1.481313; Skvortsov AM, 2001, PHYSICA A, V290, P445, DOI 10.1016-S0378-4371(00)00402-7; Skvortsov AM, 2002, EUROPHYS LETT, V58, P292, DOI 10.1209-epl-i2002-00636-0; Steels BM, 2000, J CHROMATOGR B, V743, P31, DOI 10.1016-S0378-4347(00)00199-7; Subramanian G, 1996, MACROMOLECULES, V29, P4045, DOI 10.1021-ma946439r; SUBRAMANIAN G, 1995, EUROPHYS LETT, V29, P285, DOI 10.1209-0295-5075-29-4-003; WILLIAMS DRM, 1995, J PHYS II, V9, P1417; Zhang WK, 2000, J PHYS CHEM B, V104, P10258, DOI 10.1021-jp000459f17191
The Third Skvortsov Readings
No full textOn December 17, 2021, MGIMO University held the International Scientific Conference dedicated to the memory of Lev Ivanovich Skvortsov, outstanding linguist, lexicographer, Doctor of Philology, professor, author of many dictionaries and books on the culture of Russian spoken language. In the opening speech, his son Yaroslav Skvortsov, the Dean of the Faculty of International Journalism of MGIMO University, organizer and the permanent host of the Readings noted that the topic Do we speak Russian Correctly? Dynamics of Language Norms is also the title of Lev I. Skvortsov’s book, published 40 years ago and still topical. The Russian language still faces an influx of borrowed words, idioms and is prone to stylistic transformations induced by the media. Linguists, language teachers, journalists, and economists — all those interested in the conservation and development of the Russian language — came to the Suzdal Kremlin to discuss the current trends in language use and language teaching. The participants presented their ideas and research on various topics: Media variant of the language: from the usage to the norm (N. I. Klushina), Speech of YouTubers (E. V. Bykova), The concept of literacy in the Internet folklore (G. G. Slyshkin), Business slang in 2004 and today (Pogrebnyak E. V.) and others. By tradition, many departments of MGIMO University were presented at the conference. Editor-in-Chief of the Journal Concept: Philosophy, Religion, Culture, MGIMO Professor, Head of the Department of World Literature and Culture, writer Yury Pavlovich Simonov (Viazemsky) delivered a guest of honor speech. He remembered the deeds and ideals of Lev Ivanovich and urged everybody to find inspiration in the beauty of Russian nature that can only be described in the beautiful Russian language. This idea resonated with the director of Vladimir-Suzdal Reserve Museum S. E. Rybakov: Suzdal is the center of Russianness and is the right place to discuss its language. In the changing world, L. I. Skvortsov’s work reminds us of the importance of inspecting and rethinking norms that are to be adequate rather than rigid
Mechanical desorption of a single chain: Unusual aspects of phase coexistence at a first-order transition
No full textThe phase transition occurring when a single polymer chain adsorbed at a planar solid surface is mechanically desorbed is analyzed in two statistical ensembles. In the force ensemble, a constant force applied to the nongrafted end of the chain (that is grafted at its other end) is used as a given external control variable. In the z-ensemble, the displacement z of this nongrafted end from the surface is taken as the externally controlled variable. Basic thermodynamic parameters, such as the adsorption energy, exhibit a very different behavior as a function of these control parameters. In the thermodynamic limit of infinite chain length the desorption transition with the force as a control parameter clearly is discontinuous, while in the z-ensemble continuous variations are found. However, one should not be misled by a too-naive application of the Ehrenfest criterion to consider the transition as a continuous transition: rather, one traverses a two-phase coexistence region, where part of the chain is still adsorbed and the other part desorbed and stretched. Similarities with and differences from two-phase coexistence at vapor-liquid transitions are pointed out. The rounding of the singularities due to finite chain length is illustrated by exact calculations for the nonreversal random walk model on the simple cubic lattice. A new concept of local order parameter profiles for the description of the mechanical desorption of adsorbed polymers is suggested. This concept give evidence for both the existence of two-phase coexistence within single polymer chains for this transition and the anomalous character of this two-phase coexistence. 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Analytical theory of finite-size effects in mechanical desorption of a polymer chain
No full textWe discuss a unique system that allows exact analytical investigation of first- and second-order transitions with finite-size effects: mechanical desorption of an ideal lattice polymer chain grafted with one end to a solid substrate with a pulling force applied to the other end. We exploit the analogy with a continuum model and use accurate mapping between the parameters in continuum and lattice descriptions, which leads to a fully analytical partition function as a function of chain length, temperature (or adsorption strength), and pulling force. The adsorption-desorption phase diagram, which gives the critical force as a function of temperature, is nonmonotonic and gives rise to re-entrance. We analyze the chain length dependence of several chain properties (bound fraction, chain extension, and heat capacity) for different cross sections of the phase diagram. Close to the transition a single parameter (the product of the chain length N and the deviation from the transition point) describes all thermodynamic properties. We discuss finite-size effects at the second-order transition (adsorption without force) and at the first-order transition (mechanical desorption). The first-order transition has some unusual features: The heat capacity in the transition region increases anomalously with temperature as a power law, metastable states are completely absent, and instead of a bimodal distribution there is a flat region that becomes more pronounced with increasing chain length. The reason for this anomaly is the absence of an excess surface energy for the boundary between adsorbed and stretched coexisting phases (this boundary is one segment only): The two states strongly fluctuate in the transition point. 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Negative compressibility and nonequivalence of two statistical ensembles in the escape transition of a polymer chain
No full textAn end-tethered polymer chain compressed between two pistons undergoes an abrupt transition from a confined coil state to an inhomogeneous flowerlike conformation partially escaped from the gap. This phase transition is first order in the thermodynamic limit of infinitely long chains. A rigorous analytical theory is presented for a Gaussian chain in two ensembles: (a) the H -ensemble, in which the distance H between the pistons plays the role of the independent control parameter, and (b) the conjugate f -ensemble, in which the external compression force f is the independent parameter. Details about the metastable chain configurations are analyzed by introducing the Landau free energy as a function of the chain stretching order parameter. The binodal and spinodal lines, as well as the barrier heights between the stable and metastable states in the free energy landscape, are presented in both ensembles. In the loop region for the average force with dependence on the distance H (i.e., in the H -ensemble) a negative compressibility exists, whereas in the f -ensemble the average distance as a function of the force is strictly monotonic. The average fraction of imprisoned segments and the lateral force, taken as functions of the distance H or the average H, respectively, have different behaviors in the two ensembles. These results demonstrate a clear counterexample of a main principle of statistical mechanics, stating that all ensembles are equivalent in the thermodynamic limit. The authors show that the negative compressibility in the escape transition is a purely equilibrium result and analyze in detail the origin of the nonequivalence of the ensembles. It is argued that it should be possible to employ the escape transition and its anomalous behavior in macroscopically homogeneous, but microscopically inhomogeneous, materials. © 2007 American Institute of Physics.Balescu R., 1975, EQUILIBRIUM NONEQUIL; Baughman RH, 2003, NATURE, V425, P667, DOI 10.1038-425667a; Baughman RH, 1998, SCIENCE, V279, P1522, DOI 10.1126-science.279.5356.1522; BINNIG G, 1986, PHYS REV LETT, V56, P930, DOI 10.1103-PhysRevLett.56.930; BRAGANZA LF, 1986, BIOCHEMISTRY-US, V25, P7484, DOI 10.1021-bi00371a034; DAMMER U, 1995, SCIENCE, V267, P1173, DOI 10.1126-science.7855599; Ennis J, 1999, PHYS REV E, V60, P6906, DOI 10.1103-PhysRevE.60.6906; Ennis J, 2001, MACROMOLECULES, V34, P1908; Fisher M., 1965, NATURE CRITICAL POIN; Florin EL, 1997, J STRUCT BIOL, V119, P202, DOI 10.1006-jsbi.1997.3880; Gaub H. E., 1998, ADV MATER, V3, P316; GauthierManuel B, 1997, REV SCI INSTRUM, V68, P2486, DOI 10.1063-1.1148146; Guffond MC, 1997, LANGMUIR, V13, P5691, DOI 10.1021-la970377r; Hugel T, 2001, MACROMOLECULES, V34, P1039, DOI 10.1021-ma0009404; Hugel T, 2001, MACROMOL RAPID COMM, V22, P989, DOI 10.1002-1521-3927(20010901)22:13989::AID-MARC9893.0.CO;2-D; ISRAELACHVILI JN, 1978, J CHEM SOC FARAD T 1, V74, P975, DOI 10.1039-f19787400975; Jimenez J, 1998, LANGMUIR, V14, P2598, DOI 10.1021-la971233f; Klushin LI, 2004, PHYS REV E, V69, DOI 10.1103-PhysRevE.69.061101; Leermakers FAM, 2004, J STAT MECH-THEORY E, DOI 10.1088-1742-5468-2004-10-P10001; Leermakers FAM, 2002, MACROMOLECULES, V35, P8640, DOI 10.1021-ma020718u; Lubensky DK, 2000, PHYS REV LETT, V85, P1572, DOI 10.1103-PhysRevLett.85.1572; Maaloum M, 1999, MACROMOLECULES, V32, P4989, DOI 10.1021-ma981023p; Matsuoka H, 2001, MACROMOL RAPID COMM, V22, P51, DOI 10.1002-1521-3927(20010201)22:251::AID-MARC513.0.CO;2-5; Milchev A, 1999, PHYS CHEM CHEM PHYS, V1, P2083, DOI 10.1039-a809795j; Ortiz C, 1999, MACROMOLECULES, V32, P780, DOI 10.1021-ma981245n; Rief M, 1997, SCIENCE, V275, P1295, DOI 10.1126-science.275.5304.1295; Sevick EM, 2000, MACROMOLECULES, V33, P5743, DOI 10.1021-ma991348l; Sevick EM, 1999, MACROMOLECULES, V32, P6841, DOI 10.1021-ma990589q; Skvortsov AM, 2000, J CHEM PHYS, V112, P7238, DOI 10.1063-1.481313; Skvortsov AM, 2002, EUROPHYS LETT, V58, P292, DOI 10.1209-epl-i2002-00636-0; Steels BM, 2000, J CHROMATOGR B, V743, P31, DOI 10.1016-S0378-4347(00)00199-7; Subramanian G, 1996, MACROMOLECULES, V29, P4045, DOI 10.1021-ma946439r; Vakarin EV, 2006, J CHEM PHYS, V124, DOI 10.1063-1.2191054; Wang MD, 1998, SCIENCE, V282, P902, DOI 10.1126-science.282.5390.902; WILLIAMS DRM, 1995, J PHYS II, V9, P1417; Zhang WK, 2000, J PHYS CHEM B, V104, P10258, DOI 10.1021-jp000459f10111
The Paris Commune in Russian historiography: power, mistakes, and damages according to the ideas of Lenin and Skvortsov-Stepanov
No full text<p>After more than one hundred fifty years, the topic of the Paris Commune as a first example of a new form of government, even if it eventually proved to be fragile, is still worth scientific attention. The following work presents an outline of the moments that marked the beginning and the end of the Paris Commune, focusing on the impression perceived by V.I. Lenin and I. I. Skvortsov-Stepanov in Russian historiography about some of the structural characteristics and contradictions of this new politic and social phenomenon. The author starts from the political and economic background of France before the Franco-Prussian War, moving then on to the considerations of Lenin, as one of the most influent thinkers of pre-Soviet Russia, and Skvortsov-Stepanov, as one of the first Soviet scholars who investigated the causes and the damages suffered by Paris as an aftermath of the suppression of the Paris Commune. In the following work, the author illustrates a generous number of extracts in original language complete with professional translation. </p>
'Every book is a part of life'
No full text© 2019, I. A. Ermakova. In her interview with the critic and scholar A. Skvortsov, the poet I. Ermakova discusses modern poetry, its authors and processes. Starting as a conversation about the poet's artistic evolution and mentioning her work as a translator, author of regular publications in various think journals, and her numerous poetic prizes, the interview gradually moves on to examining the contemporary poetic reality, which Ermakova describes as 'the era of Oleg Chukhontsev'. She argues that the value of Chukhontsev's poetry lies in its absolute precision of word choice and accurate and truthful depiction of familiar reality. In such an attempt to display the world undistorted, modern poets turn to related art forms, up to the cinematic, however few reach this level. The interview, therefore, provides Ermakova's assessment of the contemporary literary environment, her views on how one can join the literary process, and contemplations about the problem of the reader of modern poetry: whether they exist, and who they are
Temperature effects in the mechanical desorption of an infinitely long lattice chain: Re-entrant phase diagrams
No full textWe consider the mechanical desorption of an infinitely long lattice polymer chain tethered at one end to an adsorbing surface. The external force is applied to the free end of the chain and is normal to the surface. There is a critical value of the desorption force ftr at which the chain desorbs in a first-order phase transition. We present the phase diagram for mechanical desorption with exact analytical solutions for the detachment curve: the dependence of ftr on the adsorption energy ε (at fixed temperature T) and on T (at fixed ε). For most lattice models ftr (T) displays a maximum. This implies that at some given force the chain is adsorbed in a certain temperature window and desorbed outside it: the stretched state is re-entered at low temperature. We also discuss the energy and heat capacity as a function of T; these quantities display a jump at the transition(s). We analyze short-range and long-range excluded-volume effects on the detachment curve ftr (T). For short-range effects (local stiffness), the maximum value of f tr decreases with stiffness, and the force interval where re-entrance occurs become narrower for stiffer chains. For long-range excluded-volume effects we propose a scaling ftr ∼ T1-v (Tc -T)v-φ around the critical temperature Tc, where v=0.588 is the Flory exponent and φ≈0.5 the crossover exponent, and we estimated the amplitude. We compare our results for a model where immediate step reversals are forbidden with recent self-avoiding walk simulations. We conclude that re-entrance is the general situation for lattice models. 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Sharp and fast: Sensors and switches based on polymer brushes with adsorption-active minority chains
No full textWe propose a design for polymer-based sensors and switches with sharp switching transition and fast response time. The switching mechanism involves a radical change in the conformations of adsorption-active minority chains in a brush. Such transitions can be induced by a temperature change of only about ten degrees, and the characteristic time of the conformational change is less than a second. We present an analytical theory for these switches and support it by self-consistent field calculations and Brownian dynamics simulations. © 2014 American Physical Society.Abdulahad AI, 2009, J POLYM SCI POL PHYS, V47, P2533, DOI 10.1002-polb.21862; CHALLA MSS, 1990, PHASE TRANSIT, V24-6, P343, DOI 10.1080-01411599008210236; Chen T, 2010, PROG POLYM SCI, V35, P94, DOI 10.1016-j.progpolymsci.2009.11.004; Cohen-Stuart M. A., 2010, NAT MATER, V9, P101; de Vos WM, 2009, POLYMER, V50, P305, DOI 10.1016-j.polymer.2008.10.025; Draper J, 2004, LANGMUIR, V20, P4064, DOI 10.1021-la0361316; Gorbunov AA, 2001, J CHEM PHYS, V114, P5366, DOI 10.1063-1.1346686; KLUSHIN LI, 1992, MACROMOLECULES, V25, P3443, DOI 10.1021-ma00039a021; KLUSHIN LI, 1991, MACROMOLECULES, V24, P1549, DOI 10.1021-ma00007a016; LAI PY, 1992, J PHYS II, V2, P547; Motornov M, 2003, LANGMUIR, V19, P8077, DOI 10.1021-la0343573; MURAT M, 1989, MACROMOLECULES, V22, P4054, DOI 10.1021-ma00200a041; Paul W., 1999, STOCHASTIC PROCESSES; Reith D, 2012, MACROMOLECULES, V45, P4381, DOI 10.1021-ma202745b; Romeis D, 2013, J CHEM PHYS, V139, DOI 10.1063-1.4816125; Romeis D., 2012, J CHEM PHYS, V137; Rubin RJ, 1965, J CHEM PHYS, V43, P2392, DOI 10.1063-1.1697138; Skvortsov AM, 1999, MACROMOLECULES, V32, P2004, DOI 10.1021-ma981401q; Skvortsov AM, 1997, MACROMOLECULES, V30, P1818, DOI 10.1021-ma961111e; ZHULINA EB, 1990, J COLLOID INTERF SCI, V137, P495, DOI 10.1016-0021-9797(90)90423-L0
Can one detach a fully adsorbed flexible polymer chain by an ultra-small external force?
No full textFull adsorption of flexible chains onto typical solid substrates occurs at a surface interaction energy of (5-10) kBT. The corresponding detachment force is in the range 10-50 pN. In contrast to bare solid substrates common to non-living materials, surfaces coated with brush-like polymer layers are very common in biological soft matter. We employ a simple mean-field approach to describe the effects of weak attraction between a floating long macromolecule and the brush. We show that even for a moderately thick brush a very small effective attraction is enough to produce complete binding of the long chain. The detachment force scales as , where W is the brush thickness. Hence the force could be 1 to 2 orders of magnitude smaller than in the case of typical solid substrates. © Copyright EPLA, 2013.ALEXANDER S, 1977, J PHYS-PARIS, V38, P983, DOI 10.1051-jphys:01977003808098300; Arita T, 2010, NANOSCALE, V2, P1467, DOI 10.1039-c0nr00157k; BHATTACHARYA S., 2008, EUR PHYS J E, V29, P285; Bhattacharya S, 2009, PHYS REV E, V79, DOI 10.1103-PhysRevE.79.030802; Bhattacharya S, 2009, MACROMOLECULES, V42, P2236, DOI 10.1021-ma8024392; Binder K, 2012, J POLYM SCI POL PHYS, V50, P1515, DOI 10.1002-polb.23168; Bockelmann U, 2002, BIOPHYS J, V82, P1537; Bruce A., 2002, MOL BIOL CELL; Chen M, 2009, SCIENCE, V323, P1698, DOI 10.1126-science.1169399; DEGENNES PG, 1980, MACROMOLECULES, V13, P1069, DOI 10.1021-ma60077a009; Hugel H, 2001, MACROMOL RAPID COMM, V22, P989; Klein J, 2006, P I MECH ENG J-J ENG, V220, P691, DOI 10.1243-13506501JET143; Klushin LI, 2013, PHYS REV E, V87, DOI 10.1103-PhysRevE.87.022604; Kufer SK, 2008, SCIENCE, V319, P594, DOI 10.1126-science.1151424; Landau L D, 1977, QUANTUM MECH NONRELA, V3; Milchev A, 2010, J CHEM PHYS, V132, DOI 10.1063-1.3414996; Pasch H, 1999, HPLC POLYM; Reitsma S, 2007, PFLUG ARCH EUR J PHY, V454, P345, DOI 10.1007-s00424-007-0212-8; Rubinstein M, 2003, POLYM PHYS; Skvortsov AM, 2010, J CHEM PHYS, V132, DOI 10.1063-1.3308626; Skvortsov AM, 2009, J CHEM PHYS, V130, DOI 10.1063-1.311060410
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