Temperature-dependent NIR-CPL spectra of chiral Yb(III) complexes.

Chiral, enantiopure Yb(III) complexes exhibit circularly polarized luminescence (CPL) in the near infrared (NIR) wavelength region. This CPL is quantified by the dissymmetry factor (glum). The excited state 2F5/2 consists of six mJ' states degenerated in three Stark levels, due to the crystal-field splitting (CFS), which are populated in accordance with the Boltzmann distribution. Consequently, room temperature CPL spectra are the sum of various - either positive or negative - contributions, that are practically impossible to quantify. To address this issue, an advanced setup enabling CPL measurements over a broad temperature range (300 to 4 K) has been developed. The interrelation of CFS, glum and temperature was explored using a pair of enantiopure Yb(III) complexes, highlighting the individual contribution of each crystal-field sublevel to the overall CPL spectrum, as anticipated by simulations performed in the framework of multireference wave-functions. Hence, the CPL spectra of chiral lanthanide complexes were found to be indeed strongly temperature-dependent, as is the glum dissymmetry factor, as a consequence of the variation in thermal sublevel population.

Acid/Base-Triggered Photophysical and Chiroptical Switching in a Series of Helicenoid Compounds.

A series of molecules that possess two quinolines, benzoquinolines, or phenanthrolines connected in a chiral fashion by a biaryl junction along with their water-soluble derivatives was developed and characterized. The influence of the structure on the basicity of the nitrogen atoms in two heterocycles was examined and the photophysical and chiroptical switching activity of the compounds upon protonation was studied both experimentally and computationally. The results demonstrated that changes in the electronic structure of the protonated vs. neutral species, promoting a bathochromic shift of dominant electronic transitions and alternation of their character from π-to-π* to charge-transfer-type, when additionally accompanied by the high structural flexibility of a system, leading to changes in conformational preferences upon proton binding, produce particularly pronounced modifications of the spectral properties in acidic medium. The latter combined with reversibility of the read-out make some of the molecules in this series very promising multifunctional pH probes.

Circularly polarized luminescence in the one-dimensional assembly of binaphtyl-based Yb(iii) single-molecule magnets.

Lanthanide ions have attracted great interest owing to their optical and magnetic properties. Single-molecule magnet (SMM) behavior has been a fascinating science for thirty years. Moreover, chiral lanthanide complexes allow the observation of remarkable circularly polarized luminescence (CPL). However, the combination of both SMM and CPL behaviors in a single molecular system is very rare and deserves attention in the design of multifunctional materials. Four chiral one-dimensional coordination compounds involving 1,1'-Bi-2-naphtol (BINOL)-derived bisphosphate ligands and the Yb(iii) centre were synthesized and characterized by powder and single-crystal X-ray diffraction. All the Yb(iii)-based polymers displayed field-induced SMM behavior with magnetic relaxation occurring by applying Raman processes and near infrared CPL in the solid state.

Theoretical and experimental analysis of circularly polarized luminescence spectrophotometers for artifact-free measurements using a single CCD camera.

Circularly polarized luminescence (CPL) is a fast growing research field as a complementary chiroptical spectroscopy alternative to the conventional circular dichroism or in the quest of devices producing circularly polarized light for different applications. Because chiroptical signals are generally lower than 0.1%, conventional chiral spectroscopies rely on polarization time modulation requiring step-by-step wavelength scanning and a long acquisition time. High throughput controls motivated the development of CPL spectrophotometers using cameras as detectors and space polarization splitting. However, CPL measurements imposes careful precautions to minimize the numerous artifacts arising from experimental imperfections. Some previous work used complex calibration procedure to this end. Here we present a rigorous Mueller analysis of an instrument based on polarizations space splitting. We show that by using one camera and combining spatial and temporal separation through two switchable circular polarization encoding arms we can record accurate CPL spectra without the need of any calibration. The measurements robustness and their fast acquisition times are exemplified on different chiral emitters.

Multifunctional Helicene-Based Ytterbium Coordination Polymer Displaying Circularly Polarized Luminescence, Slow Magnetic Relaxation and Room Temperature Magneto-Chiral Dichroism.

The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as magneto-chiral dichroism (MChD) and circularly polarized luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of YbIII were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)3 units (hfac- =1,1,1,5,5,5-hexafluoroacetylaconate), efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the YbIII induces a strong magnetic anisotropy which leads to a single-molecule magnet (SMM) behaviour and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1'-bi-2-naphtol-derived bisphosphate ligands.

The interest for lanthanide circularly polarized luminescence (CPL) has been quickly growing for 10 years. However, very few of these studies have involved correlation between the dissymmetry factor (glum ) and the chemical modifications in a series of chiral ligands. Four polymeric compounds of Eu(III) were prepared by using a series of binaphtyl derivatives for which the size of the π system as well as the number of stereogenic elements (i.e., the binaphtyl moiety) are modulated. The resulting {[Eu(hfac)3 ((S)/(R)-Lx )]}n (x = 1 and 3) and {[Eu(hfac)3 ((S,S,S)/(R,R,R)-Lx )]}n (x = 2 and 4) have been characterized by powder X-ray diffraction by comparison with the X-ray structures on single crystal of the Dy(III) analogs. In solution, the structure of the complexes is deeply modified and becomes monomeric. The nature of the ligand induces change in the shape of the CPL spectra in CH2 Cl2 solution. Furthermore, a large |glum | = 0.12 of the magnetic-dipole transition for the [Eu(hfac)3 ((S,S,S)/(R,R,R)-L2 )] complex involving the ligand with three stereogenic elements and an extended 𝜋 system has been measured. This report also shows CPL measurements in solid state for the series of {[Eu(hfac)3 ((S)/(R)-Lx )]}n (x = 1 and 3) and {[Eu(hfac)3 ((S,S,S)/(R,R,R)-Lx )]}n (x = 2 and 4) polymers.

Chiral Benzothiazole Monofluoroborate Featuring Chiroptical and Oxygen-Sensitizing Properties: Synthesis and Photophysical Studies.

Advances in personalized medicine are prompting the development of multimodal agents, that is, molecules that combine properties promoting various diagnostic and therapeutic applications. General approaches exploit chemical conjugation of therapeutic agents with contrast agents or the design of multimodal nanoplatforms. Herein, we report the design of a single molecule that exhibits potential for different diagnostic modes as well as the ability to sensitize oxygen, thus offering potential for photodynamic therapy. Exceptionally, this work involves the synthesis and chiral resolution of an enantiomeric pair of chiral monofluoroborates that contain a stereogenic boron atom. Combining experimental and theoretical chiroptical studies allowed the unambiguous determination of their absolute configuration. Photophysical investigations established the ability of this compound to sensitize oxygen even in the absence of heavy atoms within its structure. The synthesis of a chiral benzothiazole monofluoroborate paves a way to multimodal diagnostic tools (fluorescence and nuclear imaging) while also featuring potential therapeutic applications owing to its ability to activate oxygen to its singlet state for use in photodynamic therapy.

Dynamic and features of SARS-CoV-2 infection in Gabon.

In a context where SARS-CoV-2 population-wide testing is implemented, clinical features and antibody response in those infected have never been documented in Africa. Yet, the information provided by analyzing data from population-wide testing is critical to understand the infection dynamics and devise control strategies. We described clinical features and assessed antibody response in people screened for SARS-CoV-2 infection. We analyzed data from a cohort of 3464 people that we molecularly screened for SARS-CoV-2 infection in our routine activity. We recorded people SARS-CoV-2 diagnosis, age, gender, blood types, white blood cells (WBC), symptoms, chronic disease status and time to SARS-CoV-2 RT-PCR conversion from positive to negative. We calculated the age-based distribution of SARS-CoV-2 infection, analyzed the proportion and the spectrum of COVID-19 severity. Furthermore, in a nested sub-study, we screened 83 COVID-19 patients and 319 contact-cases for anti-SARS-CoV-2 antibodies. Males and females accounted for respectively 51% and 49% of people screened. The studied population median and mean age were both 39 years. 592 out of 3464 people (17.2%) were diagnosed with SARS-CoV-2 infection with males and females representing, respectively, 53% and 47%. The median and mean ages of SARS-CoV-2 infected subjects were 37 and 38 years respectively. The lowest rate of infection (8%) was observed in the elderly (aged > 60). The rate of SARS-Cov-2 infection in both young (18-35 years old) and middle-aged adults (36-60 years old) was around 20%. The analysis of SARS-CoV-2 infection age distribution showed that middle-aged adults accounted for 54.7% of SARS-CoV-2 positive persons, followed respectively by young adults (33.7%), children (7.7%) and elderly (3.8%). 68% (N = 402) of SARS-CoV-2 infected persons were asymptomatic, 26.3% (N = 156) had influenza-like symptoms, 2.7% (N = 16) had influenza-like symptoms associated with anosmia and ageusia, 2% (N = 11) had dyspnea and 1% (N = 7) had respiratory failure, which resulted in death. Data also showed that 12% of SARS-CoV-2 infected subjects, had chronic diseases. Hypertension, diabetes, and asthma were the top concurrent chronic diseases representing respectively 58%, 25% and 12% of recorded chronic diseases. Half of SARS-CoV-2 RT-PCR positive patients were cured within 14 days following the initiation of the anti-COVID-19 treatment protocol. 78.3% of COVID-19 patients and 55% of SARS-CoV-2 RT-PCR confirmed negative contact-cases were positive for anti-SARS-CoV-2 antibodies. Patients with severe-to-critical illness have higher leukocytes, higher neutrophils and lower lymphocyte counts contrarily to asymptomatic patients and patients with mild-to-moderate illness. Neutrophilic leukopenia was more prevalent in asymptomatic patients and patients with mild-to-moderate disease for 4 weeks after diagnosis (27.1-42.1%). In Patients with severe-to-critical illness, neutrophilic leukocytosis or neutrophilia (35.6-50%) and lymphocytopenia (20-40%) were more frequent. More than 60% of participants were blood type O. It is also important to note that infection rate was slightly higher among A and B blood types compared with type O. In this African setting, young and middle-aged adults are most likely driving community transmission of COVID-19. The rate of critical disease is relatively low. The high rate of anti-SARS-CoV-2 antibodies observed in SARS-CoV-2 RT-PCR negative contact cases suggests that subclinical infection may have been overlooked in our setting.

Circulating anti-SARS-CoV-2 nucleocapsid (N)-protein antibodies and anti-SARS-CoV-2 spike (S)-protein antibodies in an African setting: herd immunity, not there yet!

OBJECTIVE: Herd immunity is achieved when in a population, immune individuals are in a sufficiently large proportion. Neutralizing antibodies specific to SARS-CoV-2 that are produced following infection or vaccination are critical for controlling the spread of COVID-19. The objective of the present work was to investigate the rate of SARS-CoV-2 natural immunization in Gabonese. RESULTS: One thousand, four hundred and ninety two people were enrolled. The overall prevalence of anti-SARS-CoV-2 antibodies was 36.2%. Moreover, 76.4% of people who developed a humoral response to SARS-CoV-2 produced both anti-SARS-CoV-2 N-protein antibodies and anti-SARS-CoV-2 S-protein antibodies, which correspond to 27.7% of the total population. In infants (0-9 month), children (1-17 years) and adults, the prevalence of anti-SARS-CoV-2 antibodies was relatively the same, between 33 and 37% (any antibody types) and between 25 and 28.6% (neutralizing antibodies). In this African context, one-third (1/3) of the screened population was exposed to SARS-CoV-2 and three-quarter (3/4) of those exposed individuals developed neutralizing antibodies against SARS-CoV-2. This data suggest that herd immunity is not yet to be achieved in Gabon.

Rare-earth doped micro-emitters made by lift-off processing in pulsed laser deposited layers on Si substrate.

Rare earth emitters are promising in integrated optics but require complex integration on silicon. In this work, we have fabricated an Y2O3:Eu3+ micro-emitter on SiO2 on Si substrate without etching. Since pulsed laser deposition produces a high quality layer at room temperature, material can be locally deposited on top of substrates by lift-off processing. After annealing, microstructures exhibit good crystallographic quality with controlled dimensions for light confinement and narrow emission. This works allows envisioning rare-earth doped micro-photonic structures directly integrated on silicon without etching, which opens the way to integration of new functional materials on silicon platform.

Solid-State Near-Infrared Circularly Polarized Luminescence from Chiral YbIII -Single-Molecule Magnet.

A field-induced chiral YbIII Single-Molecule Magnet (SMM) displayed an unprecedented near-infrared circularly polarized luminescence (NIR-CPL) in the solid-state. The bridging bis(1,10-phenantro[5,6b])tetrathiafulvalene triad (L) allowed an efficient sensitization of the NIR 2 F5/2 →2 F7/2 emission while the NIR-CPL is associated to the f-f transitions of the YbIII ion bearing chiral ß-diketonate derived-camphorate ancillary ligands.

Reversible Soft Mechanochemical Control of Biaryl Conformations through Crosslinking in a 3D Macromolecular Network.

Tuning the dihedral angle (DA) of axially chiral compounds can impact biological activity, catalyst efficiency, molecular motor performance, or chiroptical properties. Herein, we report gradual, controlled, and reversible changes in molecular conformation of a covalently linked binaphthyl moiety within a 3D polymeric network by application of a macroscopic stretching force. We managed direct observation of DA changes by measuring the circular dichroism signal of an optically pure BINOL-crosslinked elastomer network. Stretching the elastomer resulted in a widening of the DA between naphthyl rings when the BINOL was doubly grafted to the elastomer network; no effect was observed when a single naphthyl ring of the BINOL was grafted to the elastomer network. We have determined that ca. 170 % extension of the elastomers led to the transfer of a mechanical force to the BINOL moiety of 2.5 kcal mol-1 Å-1 (ca. 175 pN) in magnitude and results in the opening of the DA of BINOL up to 130°.

Modulation of Chiroptical Properties in a Series of Helicene-like Compounds.

We describe a large-scale synthesis of a series of helicene-like compounds based on a dibenzo[c]acridine fragment by the Friedlander reaction. The series includes targeted constrained (closed) derivatives comprising 11 rings that exhibit very intense circularly polarized luminescence (CPL) (glum = 8 × 10-3) contrary to their nonconstrained (open) 10-ring precursors that are not CPL active. The relationship between structure and chiroptical properties in the series is discussed with the aid of quantum-chemical calculations.

Au10(SG)10: A Chiral Gold Catenane Nanocluster with Zero Confined Electrons. Optical Properties and First-Principles Theoretical Analysis.

We report facile synthesis of the Au10(SG)10 nanoclusters, where SG stands for glutathione, found to be promising as a new class of radiosensitizers for cancer radiotherapy. The homoleptic catenane structure with two Au5SG5 interconnected rings, among different isomer structures, gives the best agreement between theoretical and experimental optical spectra and XRD patterns. This catenane structure exhibits a centrosymmetry-broken structure, resulting in enhanced second harmonic response and new characteristic circular dichroism signals in the spectral region of 250-400 nm. This is the first determination of the nonlinear optical properties of a ligated cluster with an equal Au-to-ligand ratio, thus without a metallic core and therefore zero confined electrons. Insight into the nonlinear and chiroptical efficiencies arising from interplay between structural and electronic properties is provided by the TD-DFT approach.

Large-Scale Synthesis of Helicene-Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity.

Helicenes are fascinating molecules owing to their unusual properties and applications in many fields from catalysis to organic electronics. Herein, we report a straightforward pathway for the synthesis of helicene-like molecules on a gram scale in an enantiopure form. Thin-film materials with good propagating optical properties and very high chiroptical responses have been grown by using pulsed laser ablation without altering the structure or the enantiopurity of the molecules. Moreover, electronic and vibrational circular dichroism spectroscopies coupled with theoretical calculations enabled some dependences of the chiroptical properties with the structure to be highlighted, for example, effects of rigidification, aromatization, or the state of matter (liquid versus solid).

Efficient dibenzo[c]acridine helicene-like synthesis and resolution: scaleup, structural control, and high chiroptical properties.

Herein, we describe our recent expeditious synthesis of dibenzo[c]acridine helicene-like compounds on a large scale in pure enantiomeric form. This flexible synthesis allows for variation at several positions on the skeleton. Geometrical parameters related to these compounds have been obtained from monocrystal X-ray structure resolution. Additionally, chiroptical parameters have been recorded, highlighting the versatility of this family showing for example optical rotation at 589 nm varying between 135 and 150 deg g(-1)cm(2).

Propagation losses and gain measurements in erbium-doped fluoride glass channel waveguides by use of a double-pass technique.

We have studied Er3+, Yb3+, and Ce3+ codoped microchannel waveguides that were developed by two methods: ionic exchange for heavy metal fluoride glasses [ZrF4-BaF2-AlF3-CeF3 (ZBAC)] and vapor phase deposition for transition metal fluoride glasses [PbF2-ZnF2-GaF3 (PZG)] by using a double-pass technique. For the first time to our knowledge, the measurement of propagation losses and amplification tests were carried out by use of the same experimental setup, leading to complete characterization of the waveguides. Net gains higher than 1 dB/cm were achieved in ZBAC Er/Ce single-mode fluoride glass waveguides.