A study of the ozonolysis of isoprene in a cryogenic buffer gas cell by high resolution microwave spectroscopy

We have developed a method to quantify reaction product ratios using high resolution microwave spectroscopy in a cryogenic buffer gas cell. We demonstrate the power of this method with the study of the ozonolysis of isoprene, CH2=C(CH3)-CH=CH2, the most abundant, non-methane hydrocarbon emitted into the atmosphere by vegetation. Isoprene is an asymmetric diene, and reacts with O3 at the 1,2 position to produce methyl vinyl ketone (MVK), formaldehyde, and a pair of carbonyl oxides: [CH3CO-CH=CH2 + CH2=OO] + [CH2=O + CH3COO-CH=CH2]. Alternatively, O3 could attack at the 3,4 position to produce methacrolein (MACR), formaldehyde, and two carbonyl oxides [CH2=C(CH3)-CHO + CH2=OO] + [CH2=O + CH2=C(CH3)-CHOO]. Purified O3 and isoprene were mixed for approximately 10 seconds under dilute (1.5-4% in argon) continuous flow conditions in an alumina tube held at 298 K and 5 Torr. Products exiting the tube were rapidly slowed and cooled within the buffer gas cell by collisions with cryogenic (4-7 K) He. High resolution chirped pulse microwave detection between 12 and 26 GHz was used to achieve highly sensitive (ppb scale), isomer-specific product quantification. We observed a ratio of MACR to MVK of 2.1 +/- 0.4 under 1:1 ozone to isoprene conditions and 2.1 +/- 0.2 under 2:1 ozone to isoprene conditions, a finding which is consistent with previous experimental results. Additionally, we discuss relative quantities of formic acid (HCOOH), an isomer of CH2=OO, and formaldehyde (CH2=O) under varying experimental conditions, and characterize the spectroscopic parameters of the singly-substituted 13C trans-isoprene and 13C anti-periplanar-methacrolein species. This work has the potential to be extended towards a complete branching ratio analysis, as well towards the ability to isolate, identify, and quantify new reactive intermediates in the ozonolysis of alkenes

High Sensitivity Microwave Spectroscopy in a Cryogenic Buffer Gas Cell

We describe an instrument which can be used to analyze complex chemical mixtures at high resolution and high sensitivity. Molecules are collisionally cooled with helium gas at cryogenic temperatures (~ 4-7 K), and subsequently detected using chirped pulse microwave spectroscopy. Here we demonstrate three significant improvements to the apparatus relative to an earlier version: (1) extension of its operating range by more than a factor of two, from 12-18 GHz to 12-26 GHz, which allows a much wider range of species to be characterized; (2) improved detection sensitivity owing to use of cryogenically-cooled low-noise amplifiers and protection switches, and (3) a versatile method of sample input that enables analysis of solids, liquids, gases, and solutions, without the need for chemical separation (as demonstrated with a 12-16 GHz spectrum of lemon oil). This instrument can record broadband microwave spectra at comparable sensitivity to high Q cavity spectrometers which use pulsed supersonic jets, but up to 3000 times faster with a modest increase in sample consumption rate.Comment: 12 pages, 6 figure

The molecular structure of gauche-1,3-butadiene: Experimental proof of non-planarity

International audienceThe planarity of the second stable conformer of 1,3-butadiene-the archetypal diene for the Diels-Alder reaction, in which a planar conjugated diene and a dienophile combine to form a ring-is not established. The most recent high level calculations predict the species to adopt a twisted, gauche structure due to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the doubled bonds. Here we unambiguously prove experimentally that the structure cis-1,3-butadiene is indeed gauche with a substantial dihedral angle of 34° , in excellent agreement with theory. Observation of two tunneling components indicates that the molecule undergoes facile interconversion between two equivalent enantiomeric forms. Comparison of experimentally determined structures for gauche-and trans-butadiene provides an opportunity to examine the effects of conjugation and steric interactions

The Intraocular Cytokine Profile and Therapeutic Response in Persistent Neovascular Age-Related Macular Degeneration

Citation: Rezar-Dreindl S, Sacu S, Eibenberger K, et al. The intraocular cytokine profile and therapeutic response in persistent neovascular agerelated macular degeneration. Invest Ophthalmol Vis Sci. 2016;57:4144-4150. DOI:10.1167/iovs.16-19772 PURPOSE. To investigate the course of inflammatory and angiogenic cytokines in the aqueous humor of patients with persistent/recurrent neovascular age-related macular degeneration (nAMD) under ranibizumab monotherapy (IVM) or ranibizumab plus dexamethasone combination treatment. METHODS. In this 12-month prospective study, 40 eyes with nAMD were treated with either IVM or combined treatment with ranibizumab plus intravitreal dexamethasone implant (IVC). Patients in the IVM group were treated following an ''as needed'' treatment regimen; patients in the IVC group received ranibizumab and a dexamethasone implant at baseline and were retreated with ranibizumab. At baseline and at each time of retreatment aqueous humor samples were taken. RESULTS. Before treatment, levels of macrophage chemoattractant protein (MCP)-1, monokine induced by c interferon (MIG), and lipocalin-2/ neutrophil gelatinase-associated lipocalin (NGAL) were elevated in nAMD patients compared to healthy controls (P ¼ 0.024; P ¼ 0.04; P ¼ 0.01). In contrast, tumor necrosis factor a, IL-12p70, and secreted protein acidic and rich in cysteine (SPARC) concentrations were lower (P ¼ 0.001; P ¼ 0.008; P ¼ 0.03), while vascular endothelial growth factor (VEGF) was not altered (45 6 6/51 6 12 pg/mL nAMD/ control group; P ¼ 0.6). During IVC, levels of VEGF, MIG, platelet-derived growth factor (PDGF)-AA, and transforming growth factor b1 (P ¼ 0.005; P ¼ 0.011; P ¼ 0.008; P ¼ 0.013) were reduced. Ranibizumab monotherapy did not influence the course of any inflammatory/ angiogenic cytokine. Interleukin 6 and PDGF-AA levels correlated with central retinal thickness changes (P ¼ 0.007; P ¼ 0.022). Over the 12-month period visual function was maintained with no significant differences during or between both treatment groups. CONCLUSIONS. Inflammatory proteins are involved in the pathogenesis of chronic macular edema due to AMD and are associated with disease activity. During combined treatment, levels of inflammatory and angiogenic cytokines decreased over a 12-month period with no superiority in functional outcome

A Quantum Ruler for Magnetic Deflectometry

Matter-wave near-field interference can imprint a nano-scale fringe pattern onto a molecular beam, which allows observing its shifts in the presence of even very small external forces. Here we demonstrate quantum interference of the pre-vitamin 7-dehydrocholesterol and discuss the conceptual challenges of magnetic deflectometry in a near-field interferometer as a tool to explore photochemical processes within molecules whose center of mass is quantum delocalized

Quantum interference distinguishes between constitutional isomers

Matter waves, as introduced by de Broglie in 1923 (L. de Broglie, Nature, 1923, 112, 540),1 are a fundamental quantum phenomenon, describing the delocalized center of mass motion of massive bodies and we show here their sensitivity to the mol. structure of constitutional isomers. [on SciFinder(R)

Highly Fluorous Porphyrins as Model Compounds for Molecule Interferometry

The synthesis and characterization of seven tailor-made highly fluorous porphyrin derivatives are described, as large perfluoroalkyl-functionalized organic molecules are the most complex objects for which the quantum wave nature has been observed so far. We have found, in particular, that tetrakis(pentafluorophenyl)porphyrin is a suitable starting point for a modular synthesis that is geared towards porphyrin derivatives with many peripheral fluorous chains. This allows us to tailor and optimize the sublimation features of these compounds for molecule interferometry. We have analyzed the evaporation process of one member of the series by determining the enthalpy of evaporation, as the creation of a sufficiently intense, slow molecular beam is crucial for quantum interference experiments. We present the quantum fringe pattern of a second member of the series, which we could obtain in a Kapitza?Dirac?Talbot?Lau interferometer

Matter-wave interference of particles selected from a molecular library with masses exceeding 10 000 amu

The quantum superposition principle, a key distinction between quantum physics and classical mechanics, is often perceived as a philosophical challenge to our concepts of reality, locality or space-time since it contrasts with our intuitive expectations with experimental observations on isolated quantum systems. While we are used to associating the notion of localization with massive bodies, quantum physics teaches us that every individual object is associated with a wave function that may eventually delocalize by far more than the body's own extension. Numerous experiments have verified this concept at the microscopic scale but intuition wavers when it comes to delocalization experiments with complex objects. While quantum science is the uncontested ideal of a physical theory, one may ask if the superposition principle can persist on all complexity scales. This motivates matter–wave diffraction and interference studies with large compounds in a three-grating interferometer configuration which also necessitates the preparation of high-mass nanoparticle beams at low velocities. Here we demonstrate how synthetic chemistry allows us to prepare libraries of fluorous porphyrins which can be tailored to exhibit high mass, good thermal stability and relatively low polarizability, which allows us to form slow thermal beams of these high-mass compounds, which can be detected using electron ionization mass spectrometry. We present successful superposition experiments with selected species from these molecular libraries in a quantum interferometer, which utilizes the diffraction of matter–waves at an optical phase grating. We observe high-contrast quantum fringe patterns of molecules exceeding a mass of 10000 amu and having 810 atoms in a single particle