Quantum Logic Spectroscopy of Highly Charged Ions

Fundamental interactions and symmetries define the structure and properties of all matter, in particular of its small and diverse visible constituents—the atoms. The study of their distinctive spectra through precision spectroscopy is therefore a vital tool to advance our understanding of nature. Highly charged ions (HCIs) constitute the largest fraction of all atoms since every atom has as many charge states as electrons it can bind. Although most of the matter on Earth is neutral, HCIs are ubiquitous in the universe and their systematic study is essential not only for atomic physics but eminently for astrophysics, nuclear physics, and fusion research, among others. Recently, HCIs have been identified as ideal candidates for sensitive tests of physics beyond the Standard Model of particle physics and for use in future high-accuracy optical atomic clocks. However, the realization of such proposals has been hindered by the hitherto constrained laboratory control and limited spectroscopic accuracy of about parts-per-million fractional uncertainty levels. This thesis reports the first coherent laser spectroscopy of HCIs, boosting the achievable spectroscopic precision by eight orders of magnitude compared to traditional spectroscopy methods. The 2P1/2–2P3/2 fine-structure ground-state transition in highly charged 40Ar13+ at an optical wavelength of 441 nm was chosen as a proof-of-principle case. A single ion of this species was isolated from a megakelvin-hot plasma cloud and co-trapped together with a laser-cooled singly charged 9Be+ ion in a two-ion crystal, confined in the harmonic potential of a cryogenic linear Paul trap. This coupled quantum-mechanical system was then cooled to its ground state of axial motion, corresponding to the lowest temperature of a HCI ever achieved. The spectroscopy was realized by implementing quantum logic techniques which allow preparation of the quantum state of the HCI and to map its electronic state after spectroscopy onto the 9Be+ logic ion in order to detect it there with high efficiency through electron shelving. In addition to the increase of spectroscopic precision, the excited-state lifetime and g-factor were measured—the latter one to unprecedented accuracy, resolving effects from special relativity, interelectronic interactions, and quantum electrodynamics. Moreover, it settled a discrepancy between theoretical predictions. The demonstrated techniques are not limited to the specific 40Ar13+ species but universally applicable to other HCIs. Thereby, this work unlocks the potential of HCIs for unrivaled tests of fundamental physics, the search for new physics—such as a 5th force, variations of fundamental constants and dark matter candidates—as well as the use of HCIs in novel optical atomic clocks

Closed-cycle, low-vibration 4 K cryostat for ion traps and other applications

In-vacuo cryogenic environments are ideal for applications requiring both low temperatures and extremely low particle densities. This enables reaching long storage and coherence times for example in ion traps, essential requirements for experiments with highly charged ions, quantum computation, and optical clocks. We have developed a novel cryostat continuously refrigerated with a pulse-tube cryocooler and providing the lowest vibration level reported for such a closed-cycle system with 1 W cooling power for a <5 K experiment. A decoupling system suppresses vibrations from the cryocooler by three orders of magnitude down to a level of 10 nm peak amplitudes in the horizontal plane. Heat loads of about 40 W (at 45 K) and 1 W (at 4 K) are transferred from an experimental chamber, mounted on an optical table, to the cryocooler through a vacuum-insulated massive 120 kg inertial copper pendulum. The 1.4 m long pendulum allows installation of the cryocooler in a separate, acoustically isolated machine room. In the laser laboratory, we measured the residual vibrations using an interferometric setup. The positioning of the 4 K elements is reproduced to better than a few micrometer after a full thermal cycle to room temperature. Extreme high vacuum on the $10^{-15}$ mbar level is achieved. In collaboration with the Max-Planck-Intitut f\"ur Kernphysik (MPIK), such a setup is now in operation at the Physikalisch-Technische Bundesanstalt (PTB) for a next-generation optical clock experiment using highly charged ions

Algorithmic Ground-state Cooling of Weakly-Coupled Oscillators using Quantum Logic

Most ions lack the fast, cycling transitions that are necessary for direct laser cooling. In most cases, they can still be cooled sympathetically through their Coulomb interaction with a second, coolable ion species confined in the same potential. If the charge-to-mass ratios of the two ion types are too mismatched, the cooling of certain motional degrees of freedom becomes difficult. This limits both the achievable fidelity of quantum gates and the spectroscopic accuracy. Here we introduce a novel algorithmic cooling protocol for transferring phonons from poorly- to efficiently-cooled modes. We demonstrate it experimentally by simultaneously bringing two motional modes of a Be$^{+}$-Ar$^{13+}$ mixed Coulomb crystal close to their zero-point energies, despite the weak coupling between the ions. We reach the lowest temperature reported for a highly charged ion, with a residual temperature of only $T\lesssim200~\mathrm{\mu K}$ in each of the two modes, corresponding to a residual mean motional phonon number of $\langle n \rangle \lesssim 0.4$. Combined with the lowest observed electric field noise in a radiofrequency ion trap, these values enable an optical clock based on a highly charged ion with fractional systematic uncertainty below the $10^{-18}$ level. Our scheme is also applicable to (anti-)protons, molecular ions, macroscopic charged particles, and other highly charged ion species, enabling reliable preparation of their motional quantum ground states in traps

Sapucaia nut (Lecythis pisonis Cambess) and its by-products: a promising and underutilized source of bioactive compounds. Part II: phenolic compounds profile.

In this study, the profile of the bioactive compounds of sapucaia nut (Lecythis pisonis Cambess) and its byproducts have been investigated. The phenolic profile by LC-ESI-MS/MS, the total phenolic content, the condensed tannins and the antioxidant activity of the sapucaia nut and shell were determined. 14 phenolic compounds were identified in the sapucaia nut extract, primarily phenolic acids and flavonoids. Catechin, epicatechin, myricetin, ellagic acid and ferulic acid presented significant correlation to the antioxidant activity. The sapucaia shell contained 22 phenolic compounds, 13 of which were quantified. The sapucaia shell extract showed a high content of total phenolic compounds, a high condensed tannins content, and high antioxidant activity. The higher antioxidant activity of the shell can be associated with a higher content of phenolics. Overall, it can be concluded that the sapucaia nut is a raw material rich in phenolic compounds that present high antioxidant activity. The nuts and the cake may be used as a promising raw material for the food industry, while the shells could be an alternative source of natural antioxidants. Further use in the cosmetics and pharmaceutical industry may also be envisaged. 1. Introduction Lecythis pisonis

Sensitivity to New Physics of Isotope Shift Studies using the Coronal Lines of Highly Charged Calcium Ions

Promising searches for new physics beyond the current Standard Model (SM) of particle physics are feasible through isotope-shift spectroscopy, which is sensitive to a hypothetical fifth force between the neutrons of the nucleus and the electrons of the shell. Such an interaction would be mediated by a new particle which could in principle be associated with dark matter. In so-called King plots, the mass-scaled frequency shifts of two optical transitions are plotted against each other for a series of isotopes. Subtle deviations from the expected linearity could reveal such a fifth force. Here, we study experimentally and theoretically six transitions in highly charged ions of Ca, an element with five stable isotopes of zero nuclear spin. Some of the transitions are suitable for upcoming high-precision coherent laser spectroscopy and optical clocks. Our results provide a sufficient number of clock transitions for -- in combination with those of singly charged Ca$^+$ -- application of the generalized King plot method. This will allow future high-precision measurements to remove higher-order SM-related nonlinearities and open a new door to yet more sensitive searches for unknown forces and particles

Synthetic Receptors for the High-Affinity Recognition of O-GlcNAc Derivatives

The combination of a pyrenyl tetraamine with an isophthaloyl spacer has led to two new water-soluble carbohydrate receptors ("synthetic lectins"). Both systems show outstanding affinities for derivatives of N-acetylglucosamine (GlcNAc) in aqueous solution. One receptor binds the methyl glycoside GlcNAc-β-OMe with Ka ≈20,000 m(-1), whereas the other one binds an O-GlcNAcylated peptide with Ka ≈70,000 m(-1). These values substantially exceed those usually measured for GlcNAc-binding lectins. Slow exchange on the NMR timescale enabled structural determinations for several complexes. As expected, the carbohydrate units are sandwiched between the pyrenes, with the alkoxy and NHAc groups emerging at the sides. The high affinity of the GlcNAcyl-peptide complex can be explained by extra-cavity interactions, raising the possibility of a family of complementary receptors for O-GlcNAc in different contexts

Serum CA19-9 response as a surrogate for clinical outcome in patients receiving fixed-dose rate gemcitabine for advanced pancreatic cancer

The use of serial serum measurements of the carbohydrate antigen 19-9 (CA19-9) to guide treatment decisions and serve as a surrogate end point in clinical trial design requires further validation. We investigated whether CA19-9 decline represents an accurate surrogate for survival and time to treatment failure (TTF) in a cohort of 76 patients with advanced pancreatic cancer receiving fixed-dose rate gemcitabine in three separate studies. Statistically significant correlations between percentage CA19-9 decline and both overall survival and TTF were found, with median survival ranging from 12.0 months for patients with the greatest degree of biomarker decline (>75%) compared with 4.3 months in those whose CA19-9 did not decline during therapy (P<0.001). Using specific thresholds, patients with ⩾25% decline in CA19-9 during treatment had significantly better outcomes than those who did not (median survival and TTF of 9.6 and 4.6 months vs 4.4 and 1.5 months; P<0.001). Similar results were seen using both 50 and 75% as cutoff points. We conclude that serial CA19-9 measurements correlate well with clinical outcomes in this patient population, and that decline in this biomarker should be entertained for possible use as a surrogate end point in clinical trials for the selection of new treatments in this disease

Transcriptional profiling of degraded RNA in cryopreserved and fixed tissue samples obtained at autopsy

BACKGROUND: Traditional multiplexed gene expression methods require well preserved, intact RNA. Such specimens are difficult to acquire in clinical practice where formalin fixation is the standard procedure for processing tissue. Even when special handling methods are used to obtain frozen tissue, there may be RNA degradation; for example autopsy samples where degradation occurs both pre-mortem and during the interval between death and cryopreservation. Although specimens with partially degraded RNA can be analyzed by qRT-PCR, these analyses can only be done individually or at low levels of multiplexing and are laborious and expensive to run for large numbers of RNA targets. METHODS: We evaluated the ability of the cDNA-mediated Annealing, Selection, extension, and Ligation (DASL) assay to provide highly multiplexed analyses of cryopreserved and formalin fixed, paraffin embedded (FFPE) tissues obtained at autopsy. Each assay provides data on 1536 targets, and can be performed on specimens with RNA fragments as small as 60 bp. RESULTS: The DASL performed accurately and consistently with cryopreserved RNA obtained at autopsy as well as with RNA extracted from formalin-fixed paraffin embedded tissue that had a cryopreserved mirror image specimen with high quality RNA. In FFPE tissue where the cryopreserved mirror image specimen was of low quality the assay performed reproducibly on some but not all specimens. CONCLUSION: The DASL assay provides reproducible results from cryopreserved specimens and many FFPE specimens obtained at autopsy. Gene expression analyses of these specimens may be especially valuable for the study of non-cancer endpoints, where surgical specimens are rarely available