Boundary of Quantum Evolution under Decoherence

Relaxation effects impose fundamental limitations on our ability to coherently control quantum mechanical phenomena. In this letter, we establish physical limits on how closely can a quantum mechanical system be steered to a desired target state in the presence of relaxation. In particular, we explicitly compute the maximum coherence or polarization that can be transferred between coupled nuclear spins in the presence of very general decoherence mechanisms that include cross-correlated relaxation. We give analytical expressions for the control laws (pulse sequences) which achieve these physical limits and provide supporting experimental evidence. Exploitation of cross-correlation effects has recently led to the development of powerful methods in NMR spectroscopy to study very large biomolecules in solution. We demonstrate with experiments that the optimal pulse sequences provide significant gains over these state of the art methods, opening new avenues for spectroscopy of much larger proteins. Surprisingly, in spite of very large relaxation rates, optimal control can transfer coherence without any loss when cross-correlated relaxation rates are tuned to auto-correlated relaxation rates

Routine repeat head CT may not be necessary for patients with mild TBI.

Background:Routine repeat cranial CT (RHCT) is standard of care for CT-verified traumatic brain injury (TBI). Despite mixed evidence, those with mild TBI are subject to radiation and expense from serial CT scans. Thus, we investigated the necessity and utility of RHCT for patients with mild TBI. We hypothesized that repeat head CT in these patients would not alter patient care or outcomes. Methods:We retrospectively studied patients suffering from mild TBI (Glasgow Coma Scale (GCS) score 13-15) and treated at the R Adams Cowley Shock Trauma Center from November 2014 through January 2015. The primary outcome was the need for surgical intervention. Outcomes were compared using paired Student's t-test, and stratified by injury on initial CT, GCS change, demographics, and presenting vital signs (mean ± SD). Results:Eighty-five patients met inclusion criteria with an average initial GCS score=14.6±0.57. Our center sees about 2800 patients with TBI per year, or about 230 per month. This includes patients with concussions. This sample represents about 30% of patients with TBI seen during the study period. Ten patients required operation (four based on initial CT and others for worsening GCS, headaches, large unresolving injury). There was progression of injury on repeat CT scan in only two patients that required operation, and this accompanied clinical deterioration. The mean brain Abbreviated Injury Scale (AIS) score was 4.8±0.3 for surgical patients on initial CT scan compared with 3.4±0.6 (P<0.001) for non-surgical patients. Initial CT subdural hematoma size was 1.1±0.6 cm for surgical patients compared with 0.49±0.3 cm (P=0.05) for non-surgical patients. There was no significant difference between intervention groups in terms of other intracranial injuries, demographics, vital signs, or change in GCS. Overall, 75 patients that did not require surgical intervention received RHCT. At $340 per CT,$51 000 was spent on unnecessary imaging ($367 000/year, extrapolated). Discussion:In an environment of increased scrutiny on healthcare expenditures, it is necessary to question dogma and eliminate unnecessary cost. Our data questions the use of routine repeat head CT scans in every patient with anatomic TBI and suggests that clinically stable patients with small injury can simply be followed clinically. Level of evidence:Level III

Broadband Relaxation-Optimized Polarization Transfer in Magnetic Resonance

Many applications of magnetic resonance are limited by rapid loss of spin coherence caused by large transverse relaxation rates. In nuclear magnetic resonance (NMR) of large proteins, increased relaxation losses lead to poor sensitivity of experiments and increased measurement time. In this paper we develop broadband relaxation optimized pulse sequences (BB-CROP) which approach fundamental limits of coherence transfer efficiency in the presence of very general relaxation mechanisms that include cross-correlated relaxation. These broadband transfer schemes use new techniques of chemical shift refocusing (STAR echoes) that are tailored to specific trajectories of coupled spin evolution. We present simulations and experimental data indicating significant enhancement in the sensitivity of multi-dimensional NMR experiments of large molecules by use of these methods

Current needs of the pharmaceutical industry: opportunities and challenges for implementing novel drying technologies

[EN] Commercial drying methods are limited either by high production costs or significant quality loss due to process-related stresses. The near-ubiquitous use of freeze-drying in the pharmaceutical industry makes it the standard to which other drying technologies are compared. However, the shortcomings of lyophilization warrant evaluation of new techniques and the benefits they offer, such as compatibility with continuous manufacturing. Novel drying technologies must also overcome barriers to commercial implementation including, but not limited to, scalability and integration into a GMP environment. There remain several opportunities for further research which direct focus and investment strategy for the next generation pharmaceutical drying technologies.Langford, A.; Luy, B.; Ohtake, S. (2018). Current needs of the pharmaceutical industry: opportunities and challenges for implementing novel drying technologies. En IDS 2018. 21st International Drying Symposium Proceedings. Editorial Universitat Politècnica de València. 1997-2002. https://doi.org/10.4995/IDS2018.2018.8354OCS1997200

Complexity of decoupling and time-reversal for n spins with pair-interactions: Arrow of time in quantum control

Well-known Nuclear Magnetic Resonance experiments show that the time evolution according to (truncated) dipole-dipole interactions between n spins can be inverted by simple pulse sequences. Independent of n, the reversed evolution is only two times slower than the original one. Here we consider more general spin-spin couplings with long range. We prove that some are considerably more complex to invert since the number of required time steps and the slow-down of the reversed evolutions are necessarily of the order n. Furthermore, the spins have to be addressed separately. We show for which values of the coupling parameters the phase transition between simple and complex time-reversal schemes occurs.Comment: Completely rewritten, new lower bounds on the number of time steps, applications and references adde

Selective excitation enables encoding and measurement of multiple diffusion parameters in a single experiment

Band selectivity to address specific resonances in a spectrum enables one to encode individual settings for diffusion experiments. In a single experiment, this could include different gradient strengths (enabling coverage of a larger range of diffusion constants), different diffusion delays, or different gradient directions (enabling anisotropic diffusion measurement). In this report, a selective variant of the bipolar pulsed gradient eddy current delay (BPP-LED) experiment, enabling selective encoding of three resonances, was implemented. As proof of principle, the diffusion encoding gradient amplitude was assigned a range dependent on the selected signal, thereby allowing the extraction of the diffusion coefficient for water and a tripeptide (Met-Ala-Ser) with optimal settings in a single experiment

Rhodium(I) and Iridium(I) complexes of the conformationally rigid IBioxMe4Ligand : computational and experimental studies of unusually tilted NHC coordination geometries

Computational methods have been used to analyze distorted coordination geometries in a coherent range of known and new rhodium(I) and iridium(I) complexes containing bioxazoline-based NHC ligands (IBiox). Such distortions are readily placed in context of the literature through measurement of the Cnt(NHC)–CNCN–M angle (ΘNHC; Cnt = ring centroid). On the basis of restricted potential energy calculations using cis-[M(IBioxMe4)(CO)2Cl] (M1; M = Rh, Ir), in-plane (yawing) tilting of the NHC was found to incur significantly steeper energetic penalties than orthogonal out-of-plane (pitching) movement, which is characterized by noticeably flat potential energy surfaces. Energy decomposition analysis (EDA) of the ground-state and pitched structures of M1 indicated only minor differences in bonding characteristics. In contrast, yawing of the NHC ligand is associated with a significant increase in Pauli repulsion (i.e., sterics) and reduction in M→NHC π back donation, but is counteracted by supplemental stabilizing bonding interactions only possible due to the closer proximity of the methyl substituents with the metal and ancillary ligands. Aided by this analysis, comparison with a range of carefully selected model systems and EDA, distorted coordination modes in trans-[M(IBioxMe4)2(COE)Cl] (M2; M = Rh, Ir) and [M(IBioxMe4)3]+ (M3; M = Rh, Ir) have been rationalized. Steric interactions were identified as the major contributing factor and are associated with a high degree of NHC pitching. In the case of Rh3, weak agostic interactions also contribute to the distortions, particularly with respect to NHC yawing, and are notable for increasing the bond dissociation energy of the distorted ligands. Supplementing the computational analysis, an analogue of the formally 14 VE Rh(I) species Rh3 bearing the cyclohexyl-functionalized IBiox6 ligand ([Rh(IBiox6)3]+, Rh3-Cy) was prepared and found to exhibit an exceptionally distorted NHC ligand (ΘNHC = 155.7(2)°) in the solid state