Generation of charged droplets by field ionization of liquid helium

Positively charged helium droplets were produced by ionization of liquid helium in an electrostatic spraying experiment, in which fluid emerging from a thin glass capillary was ionized by applying a high voltage to a needle inside the capillary. At 2.2 K, fine droplets (<10 mu m in diameter) were produced in pulsed sprays or showers with total currents as high as 0.4 mu A at relatively low voltages (2-4 kV). Ionization was accompanied by a visible glow at the needle and glass tips. Droplet formation was suppressed at 3.5 K. In contrast, liquid nitrogen formed a well-defined Taylor cone with droplets having diameters comparable to the jet (approximate to 100 mu m) at much lower currents (3 nA) and higher voltages (9 kV), in agreement with previous results. The mechanism for charging in these liquids was proposed to be field ionization, identical to the processes leading to conduction in cryogenic insulating liquids observed by Gomer. The high currents resulting from field ionization in helium, together with the intrinsically low surface tension of helium I, led to charge densities that greatly exceeded the Rayleigh limit, thus preventing formation of a Taylor cone and resulting in Coulomb explosion of the liquid

Electronic spectroscopy of the alkaline-earth halide cluster Ca_2Cl_3

A visible spectrum of the cluster Ca_2Cl_3 was observed from 651 to 630 nm by 1 + 1[prime] resonant multiphoton ionization spectroscopy. Spectra were obtained for each of the four isotopomers: Ca2 35Cl3, Ca2 35Cl2 37Cl, Ca2 35Cl 37Cl2, and Ca2 37Cl3. The spectra were composed of a strong origin band at 15 350.8 cm^(–1) and several very weak vibronic bands. All of the bands were sharp with partially resolved rotational band contours. Density functional calculations predicted three minimum energy isomers. The spectrum was assigned to the 2B2<--X-tilde 2A1 transition of the lowest energy isomer, a planar C2v structure having a ring of two Cl and two Ca atoms and a terminal Cl atom. The ring isomer of Ca_2Cl_3 has the unpaired electron localized on one Ca^(2+) ion to form a Ca^+ chromophore. The two other predicted isomers, a D3h trigonal bipyramid and a C2v planar V-shaped structure, were not consistent with the observations

Generation of energetic He atom beams by a pulsed positive corona discharge

Time-of-flight measurements were made of neutral helium atom beams extracted from a repetitive, pulsed, positive-point corona discharge. Two strong neutral peaks, one fast and one slow, were observed, accompanied by a prompt photon peak and a fast ion peak. All peaks were correlated with the pulsing of the discharge. The two types of atoms appear to be formed by different mechanisms at different stages of the corona discharge. The fast atoms had energies of 190 eV and were formed at the onset of the pulsing, approximately 0.7 µs before the maximum of the photon peak. The slow peak, composed of electronically metastable He atoms, originated 30–50 µs after the photon pulse, and possessed a nearly thermal velocity distribution. The velocity distribution was typical of an undisturbed supersonic expansion with a stagnation temperature of 131 K and a speed ratio of 3.6. Peak intensities and velocities were measured as a function of source voltage, stagnation pressure, and skimmer voltage

Infrared Spectra of Mass-Selected Br¯−(NH_3)_n and I¯−NH_3 Clusters

Infrared vibrational predissociation spectra are recorded for Br¯−(NH_3)_n (n = 1−4) and I¯−NH_3 clusters in the N−H stretch region (3040−3460 cm^(−1)). To aid spectral assignments and clarify structures of the Br¯−(NH_3)_n clusters, ab initio calculations are performed at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVTZ levels of theory. The Br¯−NH_3 and I¯−NH_3 dimers are predicted to have structures in which the NH_3 molecule is attached to the halide anion by a single hydrogen-bond. The dominant infrared band for Br¯−NH_3 at 3171 cm^(−1) corresponds to a hydrogen-bonded N−H stretch vibrational mode, whereas two weaker bands are assigned to a symmetric stretch vibration of the nonbonded N−H groups (3347 cm^(−1)) and to an ammonia-based bending overtone (3293 cm^(−1)) deriving infrared intensity through Fermi interaction with the H-bonded N−H stretch mode. The corresponding I¯−NH3 spectrum is dominated by the H-bonded N−H stretch band at 3217 cm^(−1), with three weaker bands at 3240, 3305, and 3360 cm^(−1) assigned to two bending overtone vibrations and the nonbonded N−H symmetric stretch vibration, respectively. Spectra of the Br¯−(NH_3)_n, n = 2−4, clusters are similar to the I¯−NH_3 spectrum, exhibiting evidence for strong Fermi interactions between the H-bonded N−H stretch vibrational mode and ammonia-based bending overtones. On the basis of the infrared spectra and ab initio calculations, the larger Br¯−(NH_3)_n clusters are deduced to have structures in which the NH_3 molecules are attached to the Br¯ by single H-bonds, but not necessarily to one other

Analysis of Marker-Defined HNSCC Subpopulations Reveals a Dynamic Regulation of Tumor Initiating Properties

Head and neck squamous carcinoma (HNSCC) tumors carry dismal long-term prognosis and the role of tumor initiating cells (TICs) in this cancer is unclear. We investigated in HNSCC xenografts whether specific tumor subpopulations contributed to tumor growth. We used a CFSE-based label retentions assay, CD49f (α6-integrin) surface levels and aldehyde dehydrogenase (ALDH) activity to profile HNSCC subpopulations. The tumorigenic potential of marker-positive and -negative subpopulations was tested in nude (Balb/c nu/nu) and NSG (NOD.Cg-Prkdcscid Il2rgtm1Wjl/SzJ) mice and chicken embryo chorioallantoic membrane (CAM) assays. Here we identified in HEp3, SQ20b and FaDu HNSCC xenografts a subpopulation of G0/G1-arrested slow-cycling CD49fhigh/ALDH1A1high/H3K4/K27me3low subpopulation (CD49f+) of tumor cells. A strikingly similar CD49fhigh/H3K27me3low subpopulation is also present in primary human HNSCC tumors and metastases. While only sorted CD49fhigh/ALDHhigh, label retaining cells (LRC) proliferated immediately in vivo, with time the CD49flow/ALDHlow, non-LRC (NLRC) tumor cell subpopulations were also able to regain tumorigenic capacity; this was linked to restoration of CD49fhigh/ALDHhigh, label retaining cells. In addition, CD49f is required for HEp3 cell tumorigenicity and to maintain low levels of H3K4/K27me3. CD49f+ cells also displayed reduced expression of the histone-lysine N-methyltransferase EZH2 and ERK1/2phosphorylation. This suggests that although transiently quiescent, their unique chromatin structure is poised for rapid transcriptional activation. CD49f− cells can “reprogram” and also achieve this state eventually. We propose that in HNSCC tumors, epigenetic mechanisms likely driven by CD49f signaling dynamically regulate HNSCC xenograft phenotypic heterogeneity. This allows multiple tumor cell subpopulations to drive tumor growth suggesting that their dynamic nature renders them a “moving target” and their eradication might require more persistent strategies

Effect of aliskiren on post-discharge outcomes among diabetic and non-diabetic patients hospitalized for heart failure: insights from the ASTRONAUT trial

Aims The objective of the Aliskiren Trial on Acute Heart Failure Outcomes (ASTRONAUT) was to determine whether aliskiren, a direct renin inhibitor, would improve post-discharge outcomes in patients with hospitalization for heart failure (HHF) with reduced ejection fraction. Pre-specified subgroup analyses suggested potential heterogeneity in post-discharge outcomes with aliskiren in patients with and without baseline diabetes mellitus (DM). Methods and results ASTRONAUT included 953 patients without DM (aliskiren 489; placebo 464) and 662 patients with DM (aliskiren 319; placebo 343) (as reported by study investigators). Study endpoints included the first occurrence of cardiovascular death or HHF within 6 and 12 months, all-cause death within 6 and 12 months, and change from baseline in N-terminal pro-B-type natriuretic peptide (NT-proBNP) at 1, 6, and 12 months. Data regarding risk of hyperkalaemia, renal impairment, and hypotension, and changes in additional serum biomarkers were collected. The effect of aliskiren on cardiovascular death or HHF within 6 months (primary endpoint) did not significantly differ by baseline DM status (P = 0.08 for interaction), but reached statistical significance at 12 months (non-DM: HR: 0.80, 95% CI: 0.64-0.99; DM: HR: 1.16, 95% CI: 0.91-1.47; P = 0.03 for interaction). Risk of 12-month all-cause death with aliskiren significantly differed by the presence of baseline DM (non-DM: HR: 0.69, 95% CI: 0.50-0.94; DM: HR: 1.64, 95% CI: 1.15-2.33; P < 0.01 for interaction). Among non-diabetics, aliskiren significantly reduced NT-proBNP through 6 months and plasma troponin I and aldosterone through 12 months, as compared to placebo. Among diabetic patients, aliskiren reduced plasma troponin I and aldosterone relative to placebo through 1 month only. There was a trend towards differing risk of post-baseline potassium ≥6 mmol/L with aliskiren by underlying DM status (non-DM: HR: 1.17, 95% CI: 0.71-1.93; DM: HR: 2.39, 95% CI: 1.30-4.42; P = 0.07 for interaction). Conclusion This pre-specified subgroup analysis from the ASTRONAUT trial generates the hypothesis that the addition of aliskiren to standard HHF therapy in non-diabetic patients is generally well-tolerated and improves post-discharge outcomes and biomarker profiles. In contrast, diabetic patients receiving aliskiren appear to have worse post-discharge outcomes. Future prospective investigations are needed to confirm potential benefits of renin inhibition in a large cohort of HHF patients without D