Are the Crystal Structures of Enantiopure and Racemic Mandelic Acids Determined by Kinetics or Thermodynamics?

YesMandelic acids are prototypic chiral molecules where the sensitivity of crystallized forms (enantiopure/racemic compound/polymorphs) to both conditions and substituents provides a new insight into the factors that may allow chiral separation by crystallization. The determination of a significant number of single crystal structures allows the analysis of 13 enantiopure and 30 racemic crystal structures of 21 (F/Cl/Br/CH3/CH3O) substituted mandelic acid derivatives. There are some common phenyl packing motifs between some groups of racemic and enantiopure structures, although they show very different hydrogen-bonding motifs. The computed crystal energy landscape of 3-chloromandelic acid, which has at least two enantiopure and three racemic crystal polymorphs, reveals that there are many more possible structures, some of which are predicted to be thermodynamically more favorable as well as slightly denser than the known forms. Simulations of mandelic acid dimers in isolation, water, and toluene do not differentiate between racemic and enantiopure dimers and also suggest that the phenyl ring interactions play a major role in the crystallization mechanism. The observed crystallization behavior of mandelic acids does not correspond to any simple “crystal engineering rules” as there is a range of thermodynamically feasible structures with no distinction between the enantiopure and racemic forms. Nucleation and crystallization appear to be determined by the kinetics of crystal growth with a statistical bias, but the diversity of the mandelic acid crystallization behavior demonstrates that the factors that influence the kinetics of crystal nucleation and growth are not yet adequately understood.EPSRC, Max Planck Society for the Advancement of Sciences, UCL-MPS Impact Ph.D. Fellowship, EU COST Actio

Possibility of \Lambda\Lambda pairing and its dependence on background density in relativistic Hartree-Bogoliubov model

We calculate a \Lambda\Lambda pairing gap in binary mixed matter of nucleons and \Lambda hyperons within the relativistic Hartree-Bogoliubov model. Lambda hyperons to be paired up are immersed in background nucleons in a normal state. The gap is calculated with a one-boson-exchange interaction obtained from a relativistic Lagrangian. It is found that at background density \rho_{N}=2.5\rho_{0} the \Lambda\Lambda pairing gap is very small, and that denser background makes it rapidly suppressed. This result suggests a mechanism, specific to mixed matter dealt with relativistic models, of its dependence on the nucleon density. An effect of weaker \Lambda\Lambda attraction on the gap is also examined in connection with revised information of the \Lambda\Lambda interaction.Comment: 8 pages, 6 figures, REVTeX 4; substantially rewritten, emphasis is put on the LL pairing in pure neutron matte

In medium T-matrix for superfluid nuclear matter

We study a generalized ladder resummation in the superfluid phase of the nuclear matter. The approach is based on a conserving generalization of the usual T-matrix approximation including also anomalous self-energies and propagators. The approximation here discussed is a generalization of the usual mean-field BCS approach and of the in medium T-matrix approximation in the normal phase. The numerical results in this work are obtained in the quasi-particle approximation. Properties of the resulting self-energy, superfluid gap and spectral functions are studied.Comment: 38 pages, 19 figures, Introduction rewritten, Refs. adde

Self-Consistent Quasi-Particle RPA for the Description of Superfluid Fermi Systems

Self-Consistent Quasi-Particle RPA (SCQRPA) is for the first time applied to a more level pairing case. Various filling situations and values for the coupling constant are considered. Very encouraging results in comparison with the exact solution of the model are obtained. The nature of the low lying mode in SCQRPA is identified. The strong reduction of the number fluctuation in SCQRPA vs BCS is pointed out. The transition from superfluidity to the normal fluid case is carefully investigated.Comment: 23 pages, 18 figures and 1 table, submitted to Phys. Rev.

Age at first birth in women is genetically associated with increased risk of schizophrenia

Prof. Paunio on PGC:n jäsenPrevious studies have shown an increased risk for mental health problems in children born to both younger and older parents compared to children of average-aged parents. We previously used a novel design to reveal a latent mechanism of genetic association between schizophrenia and age at first birth in women (AFB). Here, we use independent data from the UK Biobank (N = 38,892) to replicate the finding of an association between predicted genetic risk of schizophrenia and AFB in women, and to estimate the genetic correlation between schizophrenia and AFB in women stratified into younger and older groups. We find evidence for an association between predicted genetic risk of schizophrenia and AFB in women (P-value = 1.12E-05), and we show genetic heterogeneity between younger and older AFB groups (P-value = 3.45E-03). The genetic correlation between schizophrenia and AFB in the younger AFB group is -0.16 (SE = 0.04) while that between schizophrenia and AFB in the older AFB group is 0.14 (SE = 0.08). Our results suggest that early, and perhaps also late, age at first birth in women is associated with increased genetic risk for schizophrenia in the UK Biobank sample. These findings contribute new insights into factors contributing to the complex bio-social risk architecture underpinning the association between parental age and offspring mental health.Peer reviewe

Effects of multilevel posterior ligament dissection after spinal instrumentation on adjacent segment biomechanics as a potential risk factor for proximal junctional kyphosis: a biomechanical study

BACKGROUND: Spinous processes and posterior ligaments, such as inter- and supraspinous ligaments are often sacrificed either deliberately to harvest osseous material for final spondylodesis e.g. in deformity corrective surgery or accidentally after posterior spinal instrumentation. This biomechanical study evaluates the potential destabilizing effect of a progressive dissection of the posterior ligaments (PL) after instrumented spinal fusion as a potential risk factor for proximal junctional kyphosis (PJK). METHODS: Twelve calf lumbar spines were instrumented from L3 to L6 (L3 = upper instrumented vertebra, UIV) and randomly assigned to one of the two study groups (dissection vs. control group). The specimens in the dissection group underwent progressive PL dissection, followed by cyclic flexion motion (250 cycles, moment: + 2.5 to + 20. 0 Nm) to simulate physical activity and range of motion (ROM) testing of each segment with pure moments of ±15.0 Nm after each dissection step. The segmental ROM in flexion and extension was measured. The control group underwent the same loading and ROM testing protocol, but without PL dissection. RESULTS: In the treatment group, the normalized mean ROM at L2-L3 (direct adjacent segment of interest, UIV/UIV + 1, PJK-level) increased to 104.7%, 107.3%, and 119.4% after dissection of the PL L4–L6, L3–L6, and L2–L6, respectively. In the control group the mean ROM increased only to 103.2%, 106.7%, and 108.7%. The ROM difference at L2-L3 with regard to the last dissection of the PL was statistically significant (P = 0.017) and a PL dissection in the instrumented segments showed a positive trend towards an increased ROM at UIV/UIV + 1. CONCLUSIONS: A dissection of the PL at UIV/UIV + 1 leads to a significant increase in ROM at this level which can be considered to be a risk factor for PJK and should be definitely avoided during surgery. However, a dissection of the posterior ligaments within the instrumented segments while preserving the ligaments at UIV/UIV + 1 leads to a slight but not significant increase in ROM in the adjacent cranial segment UIV/UIV + 1 in the used experimental setup. Using this experimental setup we could not confirm our initial hypothesis that the posterior ligaments within a long posterior instrumentation should be preserved