We present a comprehensive study of chiral fluctuations in the reference helimagnet MnSi by polarized neutron scattering and Neutron Spin Echo spectroscopy, which reveals the existence of a completely left-handed and dynamically disordered phase. This phase may be identified as a spontaneous skyrmion phase: it appears in a limited temperature range just above the helical transition TC and coexists with the helical phase at TC .Chirality is ubiquitous in nature and of fundamental importance both on the microscopic level and in our everyday life. The break of symmetry between right and left manifests itself in parity violation, governs biological structures such as DNA and can also be experienced in the organisation of our own body. In magnetism, chirality is evident in solitons [1], systems with geometric frustration [2] and metallic systems with noncentro-symmetric lattice structures, where the resulting anti-symmetric Dzyaloshinski-Moriya (DM) interactions [3,4] introduce a parity breaking term in the Hamiltonian [5]. The DM term has the form M × ( ∇ × M ) and is more than a perturbation giving rise to the peculiar canted magnetic arrangements found in high temperature superconductors [6] or the cycloid spin structures in multiferroics [7,8]. In the non-centrosymmetric weak itinerant-electron ferromagnet MnSi, DM induced chirality comes in close interplay with Fermi liquid behavior and quantum fluctuations [9]. The Hamiltonian of MnSi comprises three hierarchically ordered magnetic interaction terms with well separated energy scales [10], which allow to distinguish between different contributions. The strongest ferromagnetic exchange interaction aligns the spins, the weaker chiral Dzyaloshinski-Moriya (DM) term twists them into a helix and the weakest Anisotropic Exchange (AE) or crystal field term pins the helix propagation vector τ along the 111 crystallographic directions.The helical order appears below T C ≈ 29 K. It is a lefthanded helix with a period of ℓ ∼ 175Å (τ ≈ 0.036Å −1 ) and all magnetic moments perpendicular to the helix vector [11].In this letter we concentrate on the chiral correlated paramagnetic or spin liquid phase of MnSi just above T C , where intense diffuse neutron scattering spreads homogeneously over the surface of a sphere with radius τ . This unusual feature emerges as a ring on the two-dimensional small angle neutron scattering patterns and the rings reduce to half-moons if the beam is polarized. This is illustrated by figure 1, which reproduces spectra from [12]. Numerous theoretical studies were devoted to explain this phase invoking possibilities such as unpinned helical order [12,13] or condensation of chiral order parameters [14]. Recent local mean-field calculations assuming the hierarchical hamiltonian of MnSi show that the helical phase is preceded by a disordered phase with skyrmionlike short range order similar to the partial order in liquid crystals [15], which sets in at T C ′ ≈ T C + 1K (see supplementary information of [15]). Skyrmions are solutions of the non-linear f...

The formation of equilibrium clusters has been studied in both a prototypical colloidal system and protein solutions. The appearance of a low-Q correlation peak in small angle scattering patterns of lysozyme solution was attributed to the cluster-cluster correlation. Consequently, the presence of long-lived clusters has been established. By quantitatively analyzing both the SANS (small angle neutron scattering) and NSE (neutron spin echo) data of lysozyme solution using statistical mechanics models, we conclusively show in this paper that the appearance of a low-Q peak is not a signature of the formation of clusters. Rather, it is due to the formation of an intermediate range order structure governed by a short-range attraction and a long-range repulsion. We have further studied dynamic features of a sample with high enough concentration at which clusters are formed in solution. From the estimation of the mean square displacement by using short-time and long-time diffusion coefficient measured by NSE and NMR, we find that these clusters are not permanent but have a finite lifetime longer than the time required to diffuse over a distance of a monomer diameter.

No abstract

Monoclonal antibodies (mAbs) are a major class of biopharmaceuticals. It is hypothesized that some concentrated mAb solutions exhibit formation of a solution phase consisting of reversibly self-associated aggregates (or reversible clusters), which is speculated to be responsible for their distinct solution properties. Here, we report direct observation of reversible clusters in concentrated solutions of mAbs using neutron spin echo. Specifically, a stable mAb solution is studied across a transition from dispersed monomers in dilute solution to clustered states at more concentrated conditions, where clusters of a preferred size are observed. Once mAb clusters have formed, their size, in contrast to that observed in typical globular protein solutions, is observed to remain nearly constant over a wide range of concentrations. Our results not only conclusively establish a clear relationship between the undesirable high viscosity of some mAb solutions and the formation of reversible clusters with extended open structures, but also directly observe self-assembled mAb protein clusters of preferred small finite size similar to that in micelle formation that dominate the properties of concentrated mAb solutions.

Recently, reversible cluster formation was identified as an underlying cause of anomalously large solution viscosities observed in some concentrated monoclonal antibody (mAb) formulations, which poses a major challenge to the use of subcutaneous injection for some mAbs. A fundamental understanding of the structural and dynamic origins of high viscosities in concentrated mAb solutions is thus of significant relevance to mAb applications in human health care, as well as being of scientific interest. Herein, we present a detailed investigation of an IgG1-based mAb to relate the short-time dynamics and microstructure to significant viscosity changes over a range of pharmaceutically relevant physiochemical conditions. The combination of light scattering, small-angle neutron scattering, and neutron spin echo measurement techniques conclusively demonstrates that, upon addition of Na2SO4, these antibodies form strongly bound reversible dimers at dilute concentrations that interact with each other to form large, loosely bound, transient clusters when concentrated. This hierarchical structure formation in solution causes a significant increase in the solution viscosity.