The anomalous behavior of the density of water in the range 30 K &lt;
            <i>T</i>
            &lt; 373 K

Mallamace, Francesco; Branca, C.; Broccio, Matteo; Corsaro, Carmelo; Mou, Chung‐Yuan; Chen, Sow‐Hsin

doi:10.1073/pnas.0706504104

Cited by 228 publications

(283 citation statements)

References 38 publications

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“…In the present experiments, essentially all of the mosaicity increase occurs above 200 K, where the mismatch between solvent expansion and lattice contraction is large (Mallamace et al, 2007). The largest rate of mosaicity increase occurs at temperatures (200-220 K) where the unit-cell volume is rapidly decreasing and the solvent viscosity is rapidly increasing.…”

Section: Origins Of Disorder On Coolingmentioning

confidence: 71%

“…This mismatch requires that the solvent either flows (to the crystal surface or to grain boundaries and other defective regions where the lattice is weak) or compresses. We estimate that pressures of 10-100 MPa could be generated within the crystal if negligible flow occurs, based upon the observed expansivity of the thaumatin lattice and the measured expansivity of water confined to 2 nm pores (Mallamace et al, 2007). Slower cooling allows more time before vitrification for solvent to flow and to accommodate the contracting protein lattice, and so may reduce stresses and solvent pooling in defective regions and thereby help maintain crystal order.…”

Section: Origins Of Disorder On Coolingmentioning

confidence: 99%

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Slow cooling of protein crystals

Warkentin¹,

Thorne²

2009

J Appl Crystallogr

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Cryoprotectant-free thaumatin crystals have been cooled from 300 to 100 K at a rate of 0.1 K s À1 -10 3 -10 4 times slower than in conventional flash coolingwhile continuously collecting X-ray diffraction data, so as to follow the evolution of protein lattice and solvent properties during cooling. Diffraction patterns show no evidence of crystalline ice at any temperature. This indicates that the lattice of protein molecules is itself an excellent cryoprotectant, and with sodium potassium tartrate incorporated from the 1.5 M mother liquor ice nucleation rates are at least as low as in a 70% glycerol solution. Crystal quality during slow cooling remains high, with an average mosaicity at 100 K of 0.2 . Most of the mosaicity increase occurs above $200 K, where the solvent is still liquid, and is concurrent with an anisotropic contraction of the unit cell. Near 180 K a crossover to solid-like solvent behavior occurs, and on further cooling there is no additional degradation of crystal order. The variation of B factor with temperature shows clear evidence of a protein dynamical transition near 210 K, and at lower temperatures the slope dB/dT is a factor of 3-6 smaller than has been reported for any other protein. These results establish the feasibility of fully temperature controlled studies of protein structure and dynamics between 300 and 100 K.

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Section: Origins Of Disorder On Coolingmentioning

confidence: 71%

Section: Origins Of Disorder On Coolingmentioning

confidence: 99%

Slow cooling of protein crystals

Warkentin¹,

Thorne²

2009

J Appl Crystallogr

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“…4,21 On the other hand, the degree of local order in liquid water will increase with decreasing temperature due to local bond-ordering. 45 A recent FTIR study 46 of the relative populations of high-density liquid (HDL) and low-density liquid (LDL) water in narrow silica pores confirmed that while at temperatures T 4 250 K the structure is dominated by molecules with local HDL order, at lower temperatures (T o 220 K) the molecules of local LDL geometry are dominating. Since the local structure of LDL water resembles that of ice, the freezing process will become an increasingly cooperative phenomenon involving increasingly larger clusters of an ice-like structure, so that freezing will imply the reorganisation of hydrogen bonds only at the periphery of the clusters.…”

Section: Limit Of Crystallization Of Water In Mcm-41mentioning

confidence: 98%

Melting and freezing of water in cylindrical silica nanopores

Jähnert

Chávez

Schaumann

et al. 2008

Phys. Chem. Chem. Phys.

328

394

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Freezing and melting of H 2 O and D 2 O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and 1 H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DT m can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* E 2.8 nm. It is concluded that D* represents a lower limit for firstorder melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.

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“…Inside the no-man's land, confined water exhibits a density minimum at ∼200 K (experimentally observed in confined water, ref. 30, and suggested in bulk by MD simulations, ref. 31), a C P (T) maximum at ∼230 K, and a α P (T) minimum, also at ∼230 K.…”

mentioning

confidence: 99%

“…The blue ones, corresponding to bulk water, are the same used to fit literature data (25,26). Confined water data also include the C P values measured using normal calorimetry (red dots) (28) and NMR (red triangles) (29), and the density and α P (T) measured using FTIR spectroscopy (17,30) (the density and thermal expansion coefficient data for T < 140 K are for amorphous water). Inside the no-man's land, confined water exhibits a density minimum at ∼200 K (experimentally observed in confined water, ref.…”

mentioning

confidence: 99%

Possible relation of water structural relaxation to water anomalies

Mallamace

Corsaro

Stanley

2013

Proc. Natl. Acad. Sci. U.S.A.

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The anomalous behavior of thermodynamic response functions is an unsolved problem in the physics of water. The mechanism that gives rise to the dramatic indefinite increase at low temperature in the heat capacity, the compressibility, and the coefficient of thermal expansion, is unknown. We explore this problem by analyzing both new and existing experimental data on the power spectrum S(Q, ω) of bulk and confined water at ambient pressure. When decreasing the temperature, we find that the liquid undergoes a structural transformation coinciding with the onset of an extended hydrogen bond network. This network onset seems to give rise to the marked viscoelastic behavior, consistent with the interesting possibility that the sound velocity and response functions of water depend upon both the frequency and wave vector.A lthough water is one of the simplest molecules, it is in reality a very complex liquid displaying more than 64 counterintuitive anomalies, most of which have not been adequately explained (1, 2). The best known of these is its density behavior: unlike most liquids, water displays a maximum at 4°C, and becomes less dense rather than more dense when it freezes. Other unexplained anomalies occur for response functions such as the isothermal compressibility K T , the isobaric heat capacity C P , and the thermal expansion coefficient α P . Moreover, if one extrapolates these functions into the metastable supercooled phase of water below the melting temperature (T M = 273 K at atmospheric pressure), and above the homogeneous nucleation temperature (T H ∼ 231 K), they behave as if they might diverge at a singular temperature T S ∼ 228 K (1). Water is a glassy liquid below the glass transition temperature T g ∼ 130 K (2). Immediately above T g it transforms into a highly viscous fluid and ultimately crystallizes at T X ∼ 150 K. The region between T X and T H is a "no-man's land" within which bulk liquid water cannot be studied (1). For these and other reasons, liquid water is one of the most exciting research topics, and an enormous number of studies have sought to elucidate the physical reasons for water's unusual properties.There are four current hypotheses (1), two of which have gained considerable attention: the singularity-free hypothesis (3, 4) and the liquid-liquid critical point (LLCP) hypothesis (5). The LLCP hypothesis is based on two assumptions: (i) that water displays the phenomenon of "liquid polymorphism" (6) and (ii) as T decreases, the hydrogen bonds (HBs) begin to form an open tetrahedrally coordinated HB network. If we begin with the stable liquid phase and decrease T, the HB lifetime and the cluster stability increase, and this altered local structure continues through the no-man's land down to the amorphous phase region. Amorphous solid water is widely believed to display polymorphism: below T g , low-density amorphous (LDA) and high-density amorphous (HDA) structures (7) can be transformed from one to the other by tuning the pressure. Hence liquid water may have local structural features...

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The anomalous behavior of the density of water in the range 30 K < T < 373 K

Cited by 228 publications

References 38 publications

Slow cooling of protein crystals

Slow cooling of protein crystals

Melting and freezing of water in cylindrical silica nanopores

Possible relation of water structural relaxation to water anomalies

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