RNA-Mediated interference of a cdc25 homolog in Caenorhabditis elegans results in defects in the embryonic cortical membrane, meiosis, and mitosis

Infrared spectra of a carbon dioxide sample enriched with oxygen-17 have been recorded with a resolution of about 0.0025 cm-1 in the region of the laser bands near 10 and 9 μm, using the long path difference Fourier Transform Spectrometer of the LPMA in Paris. The two laser bands of the 16O12C17O and 17O12C18O species have been analyzed for the first time. Line intensities for several isotopic species have been measured in this region and the rotationless transition dipole moments and Herman-Wallis coefficients of the corresponding bands have been reported. In particular intensities, alternation in the spectra of 17O12C17O has been analyzed. Copyright 1999 Academic Press.     

Infrared Spectrum of Ozone in the 4600 and 5300 cm-1 Regions: High Order Accidental Resonances through the Analysis of nu1 + 2nu2 + 3nu3 - nu2, nu1 + 2nu2 + 3nu3, and 4nu1 + nu3 Bands

The very weak bands nu1 + 2nu2 + 3nu3 and 4nu1 + nu3 of 16O3 have been observed for the first time, using the Fourier transform spectrometer (FTS) of Reims and the usual experimental setup providing a large product p x l of approximately 38 Torr x 36 m. The upper levels of these A-type bands which are rather close in energy (they appear respectively at 5291.722 and 5307.790 cm-1) belong to two different sets of interacting polyads. To correctly reproduce the rotation-vibration energy levels and account for the observed perturbations, both bands are treated in a dyad approximation: the (123) state in the Coriolis resonance with the (330) state, and the (401) state in the Coriolis resonance with the (024) state. The assignments of the rotation-vibration levels of the (123) state are confirmed by measurements of line positions of the hot band nu1 + 2nu2 + 3nu3 - nu2 which has also been observed for the first time. The fits are very satisfactory: the r.m.s. deviation for 249 energy levels of the (123) state is 2.4 x 10(-3) cm-1 and is 2.0 x 10(-3) cm-1 for 266 levels of the (401) state. These r.m.s. are near experimental accuracy. Transition moments for the three observed bands are determined from measured line intensities. Copyright 1997 Academic Press. Copyright 1997Academic Press     

The Interacting v6 = 2 Levels of D3Si35Cl: A Tool to Determine Ground State Constants from High-Resolution Spectra in the 440-590 and 900-1100 cm-1 Regions

High-resolution FTIR spectra of monoisotopic D3Si35Cl have been recorded in the regions 440-590 cm-1 (nu3/nu6) and 900-1100 cm-1 (2nu6/nu3 + nu6/2nu3). A detailed rovibrational study was done for the 2nu06, 2nu-/+26, and 2nu3 overtone bands and for the 2nu+/-26-nu+/-16, 2nu06-nu-/+16, and (nu3 + nu+/-16)-nu+/-16 hot bands. For the first time the interactions occurring between the v6 = 2, v3 = v6 = 1, and v3 = 2 levels of any trideuterated silyl halide have been analyzed. The (nu3 + nu+/-16)-nu+/-16 hot band served to obtain accurate energies of the v3 = v6 = 1 level, the nu3 + nu6 combination band not being detectable on our spectra. The first experimental determination of A0 and D0K for this molecule was undertaken by a well-established method, using the nu6, 2nu+/-26-nu+/-16, and 2nu-/+26 bands. Ground state energy differences DeltaK(J) = E0(J, K) - E0(J, K - 3) were calculated for K values from 2 to 16. By a least-squares fit of 163 such differences, the A0 and D0K values thus obtained were (in cm-1): A0 = 1.4278230(8) and D0K = 5.3916(31) x 10(-6). Copyright 1999 Academic Press.     

Comorbid panic disorder and major depression: implications for cognitive-behavioral therapy

The Fourier transform infrared spectrum of H3SiI has been recorded in the nu1/nu4 region from 2075 to 2315 cm-1 at an optical resolution of 2.3 x 10(-3) cm-1. The nu1/nu4 fundamental bands and the (nu1 + nu3) - nu3/(nu4 + nu3) - nu3 hot bands have been rotationally investigated. Numerous local perturbations have been observed in the nu1 and nu4 bands and in the hot bands. Without the lines involved in perturbations, more than 2900 transitions of the nu1/nu4 bands were used to determine the band origins and the vibration-rotation parameters of the nu1 = 1 and nuv4 = 1 states. A least-squares fit of 766 apparently unperturbed transitions of the hot bands gave the parameters of the nu1 = nu3 = 1 and nu4 = nu3 = 1 states. The l(2, 2) resonance in nu4 and the A1-E Coriolis coupling between nu1 and nu4 have been investigated. Most of the local perturbations have been studied individually using a simple model by which the main perturber for each resonance was identified. Copyright 1998 Academic Press.     

Analysis of the nu8 + nu9 Band of HNO3, Line Positions and Intensities, and Resonances Involving the v6 = v7 = 1 Dark State

Using a high-resolution (R = 0.0025 cm-1) Fourier transform spectrum of nitric acid recorded at room temperature in the 1100-1240 cm-1 region, it has been possible to perform a more extended analysis of the nu8 + nu9 band of HNO3 centered at 1205.7075 cm-1. As in a recent analysis of this band [W. F. Wang, P. P. Ong, T. L. Tan, E. C. Looi, and H. H. Teo, J. Mol. Spectrosc. 183, 407-413 (1997)], the Hamiltonian used for the line positions calculation takes into account, for the upper state, the DeltaK = +/-2 anharmonic resonance linking the rotational levels of the v8 = v9 = 1 "bright" vibrational state and those of the "dark" v6 = v7 = 1 vibrational state. More than 4800 lines were assigned in the nu8 + nu9 band, which involve significantly higher rotational quantum numbers than in previous works. On the other hand, and surprisingly as compared to previous studies, the nu8 + nu9 band appears to be a hybrid band. In fact, nonnegligible B-type transitions could be clearly identified among the much stronger A-type lines. Accordingly, a set of individual line intensities were measured for lines of both types and were introduced in a least-squares fit to get the A- and B-type components of the transition moment operator. Finally, a synthetic spectrum of the 8.3-μm region of HNO3 has been generated, using for the line positions and line intensities the Hamiltonian constants and the expansion of the transition moment operator which were determined in this work. In this way, the B-type and the A-type components of the nu8 + nu9 band appear to contribute for about (1/4) and (3/4), respectively, to the total band intensity. Copyright 1999 Academic Press.     

The Absorption Spectrum of H2S Between 2150 and 4260 cm-1: Analysis of the Positions and Intensities in the First (2nu2, nu1, and nu3) and Second (3nu2, nu1 + nu2, and nu2 + nu3) Triad Regions

The two triad systems of hydrogen sulfide (2nu2, nu1, and nu3 near 4 μm and 3nu2, nu1 + nu2, and nu2 + nu3 near 2.7 μm) were analyzed using 14 spectra recorded at 0.0056 and 0.011 cm-1 resolution with the McMath Fourier transform spectrometer located at Kitt Peak National Observatory. Experimental upper state levels of H232S, H234S, and H233S were obtained from assigned positions (as high as J = 20 and Ka = 15 for the main isotope). These were fitted to the A-reduced Watson Hamiltonian to determine precise sets of rotational constants through J10 and up to nine Fermi and Coriolis coupling parameters. Intensities of the two H232S triads were modeled with rms values of 2.5%, using the transformed transition moment expansion with 19 terms for 568 intensities of the first triad and 11 terms for the 526 intensities of the second triad. The second derivatives of the dipole moment with respect to normal coordinates were estimated in Debye to be: 22μx = -0.004873 (90); 12μx = 0.01372 (30); and 23μz = 0.01578 (30). This confirmed that for hydrogen sulfide some of the second derivatives are larger than the first derivatives. The calculated line intensities were summed yielding integrated band strengths (in cm-2/atm at 296 K) as follows: 0.3315 for 2nu2, 0.4522 for nu1, 0.1201 for nu3, 0.0303 for 3nu2, 1.820 for nu1 + nu2, and 2.869 for nu2 + nu3. In addition, the hot band transitions were identified in both regions. Finally, a composite database of hydrogen sulfide line parameters was predicted for the 5- to 2.5-μm region. Copyright 1998 Academic Press.     

High-Resolution Infrared Spectrum of Vinyl Fluoride at 500 cm-1

The infrared spectrum of vinyl fluoride (CH2=CHF) has been investigated in the region 390-590 cm-1 at room temperature and at a resolution of 0.0016 cm-1 using a Fourier transform spectrometer. The rovibrational analysis of the spectral features allowed us to assign about 11 000 lines (J 相似文献   

Nitrogen Broadening of Absorption Lines in the nu1, nu2, and nu3 Bands of H2S Determined by Applying an IR Diode Laser Spectrometer

With an infrared diode laser spectrometer in pulse mode we studied the N2 broadening of H2S absorption lines in the nu1, nu2, and nu3 bands. Altogether 22 lines were investigated: 16 lines from the R branch of the nu1 band (3 相似文献   

Methyl Isocyanide Hot Bands in the Region 1300-1560 cm-1

The hot bands accompanying the fundamentals nu6 and nu3 of CH3NC in the region 1300-1560 cm-1 observed in high-resolution Fourier transform recordings complemented by diode laser spectra have been analyzed. The observed transitions comprise 16 subbands of the pair of perpendicular E-E bands nu6± + nu8± - nu8± and nu7-/+ + 2nu80 - nu8± whose upper states form a Fermi dyad, 18 subbands of the A1,2-E perpendicular bands nu6-/+ + nu8± - nu8±/nu7± + 2nu8±2 - nu8± with upper states forming another Fermi dyad, and 8 subbands of the bi-parallel E-E band nu3 + nu8± - nu8±. The anharmonic, Coriolis, and l-type interactions which couple these upper states with each other and with the states nu7-/+ + 2nu8±2, nu4 + 3nu8±1, and nu4 + 3nu8±3 have been included in an 18 x 18 Hamiltonian matrix whose eigenvalues model the upper levels of the observed transitions. The values of 46 upper state spectroscopic constants and interaction constants have been adjusted by least squares to 950 observed lines. The results provide a reliable quantitative picture of the interacting states and yield accurate values for the spectroscopic constants of the various states and for the anharmonic constants x68, x68 (g68), and x38. Copyright 1997Academic Press     

Can Isotopic Substitution Change a Bright State into a Dark State? The Case of the v3 = 1 State of FClO3

High-resolution infrared spectra of monoisotopic samples of F35Cl18O3 and F37Cl18O3 have been recorded with the purpose of analyzing the nu3 fundamental at 535 cm-1. However, this band could not be observed whereas it had been seen and studied earlier in F35Cl16O3. To determine the parameters of the v3 = 1 state, indirect methods were used. Hot bands nun + nu3 - nu3 (n = 1 or 2) were first analyzed and their LSCD (Lower State Combination Differences) yielded rotational parameters of nu3. Then, with the help of nu1 + nu3, all rovibrational parameters of nu3 were obtained. Similar methods were applied to spectra of F35Cl16O3 and F37Cl16O3 to prove that the parameters of nu3 obtained in this fashion are identical to those determined directly for these isotopomers and are even more comprehensive. It is shown that the different character of nu3 in the two 18O and in the two 16O isotopomers is due to the fact that the former are much closer to a spherical top molecule ((A0 - B0)/A0 = 0.015). This is not only reflected in intensities different by two orders of magnitude but also in the very different values of alpha3B in these two pairs. Copyright 1997 Academic Press. Copyright 1997Academic Press     

Functional beta-cell mass after transplantation of human fetal pancreatic cells: differentiation or proliferation?

The absolute wavenumbers for 36 lines of the 3-0 band of 12C16O are measured from P(17) at 6271 cm-1 to R(19) at 6405 cm-1, with an uncertainty of about +/-3 x 10(-5) cm-1 (about +/-1 MHz). The experimental positions are compared with the best predicted positions from recent Dunham coefficients. Self-induced pressure lineshifts are determined and reach, at most, about -8 x 10(-3) cm-1 atm-1. Copyright 1997 Academic Press. Copyright 1997Academic Press     

Simultaneous Analysis of the 2nu2, nu1, and nu3 Bands of Hydrogen Telluride

Spectra of a natural sample of hydrogen telluride as well as a spectrum of monoisotopic H2 130Te have been recorded by means of Fourier transform spectrometry with a resolution of 0.003 cm-1 in the spectral domain 7.5-4.3 μm where it is easy to observe the main absorbing bands nu1 and nu3. We have located and assigned for the first time the 2nu2 band which appears in the lower wavenumber range of the recorded spectral domain near 1700 cm-1. It proved necessary to treat simultaneously the three states (020), (100), and (001). nu1 and nu3 are indeed Coriolis-coupled vibration-rotation bands and it was observed that a few rotational levels of (001) could not be fitted to within their experimental accuracy without considering the second-order Coriolis interaction between the rotational levels of (020) and (001). In this way all the experimental levels were calculated to within the experimental uncertainty, and precise sets of vibrational energies and rotational and coupling constants were obtained for the seven most abundant H2Te isotopic species, namely H2 130Te, H2 128Te, H2 126Te, H2 125Te, H2 124Te, H2 123Te, and H2 122Te. For the most abundant isotopic species H2 130Te the bands centers arenu0 (2nu2) = 1715.9568, nu0 (nu1) = 2065.2709, nu0 (nu3) = 2072.1101 cm-1. Copyright 1997Academic Press     

FT infrared and Raman investigation of saccharide-phosphatidylcholine interactions using novel structure probes

Conformational consequences of adduct formation between saccharides (trehalose, glucose, raffinose) and sorbitol with dipalmitoylphosphatidylcholine (DPPC) in multibilayers are revealed by relative intensity changes of the band components corresponding to the nu asN(CH3)3 and nu sC-N(CH3)3 stretching modes of the choline chain terminal and those of the nu C = O band. The conformational sensitivity of those modes was demonstrated previously (J. Grdadolnik et al., Chem. Phys. Lipids 65 (1993) 121) and used to demonstrate the effects of stepwise hydration of phosphatidylcholines. The latter are compared with the effects of saccharide binding and found to be qualitatively similar, but not identical. The same is true of the low frequency shifts of the nu asPO2- vibration: the shifts due to saccharide binding correspond to the binding of six to seven water molecules per phosphate which is about 20 cm-1 less than the shift caused by full hydration. A particularly interesting finding concerns the appearance of two bands in the nu asPO2- region of the DPPC-saccharide adducts. The relative intensities of the two bands (1243 and 1223 cm-1) change on additional hydration; it is the one at 1223 cm-1 that prevails at high hydration levels. Major changes in saccharide conformation are not detectable but minor differences between the DPPC bound and crystal spectra are observed.     

Neurotrophic effects of BDNF and CNTF, alone and in combination, on postnatal day 5 rat acoustic ganglion neurons

The effects of encapsulating bovine hemoglobin (BHb) in the bicontinuous cubic phase formed by monooleoylglycerol and water was investigated with Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction. Cubic phase was formed in the presence of 1-10 wt% BHb. Studies using X-ray diffraction reveal that at 0.5-2.5 wt% BHb, the cubic phase structure is characterized by the double diamond lattice (Pn3m). At 2.5-5 wt% BHb, coexistence of two cubic phase structures, Pn3m and the gyroid lattice (Ia3d), was observed while at BHb, concentrations higher than 5 wt% the gyroid structure persists. FTIR shows there is an increase in intensity of the free nu C = O (1745 cm-1) and a corresponding decrease in the intensity of the hydrogen bonded nu C = O (1720 cm-1) as the BHb concentration is increased. The nu C-O-CO peak shifts from 1183 cm-1 to 1181 cm-1 as the concentration of BHb raised from 2.5 to 10 wt% indicating BHb may induce subtle changes in the interfacial region of cubic phase monoolein. The bandwidth of the nu asCH2 stretch (2926 cm-1) increased in the presence of 5 wt% BHb compared to samples with 2.5 or 10 wt% BHb. The increase in frequency of the nu sCH2 stretch (2854 cm-1) induced by increasing temperature 20 to 60 degrees C was dampened when BHb was present compared to samples heated in isotonic buffer. Analysis of the amide I band at 1650 cm-1 showed that the secondary structure of BHb is not affected by encapsulation in monoolein. In vitro release studies showed that 45% of the entrapped BHb was released after 144 h at 37 degrees C. The porous nature of bulk cubic phase was further demonstrated by diffusion of K2Fe(CN)6 and conversion of 73% of the oxyhemoglobin to methemoglobin after 1 h. These results suggest that the cubic phase may be useful for encapsulation of Hb as a red cell substitute and for the encapsulation and delivery of other bioactive agents.     

Rotation-Vibration Constants for the nu1, nu22, nu24, nu22 + nu24, and Ground States in Pyrrole (12C4H5N)

We have recorded the infrared absorption spectrum of pyrrole at 0.005 cm-1 spectral resolution using a Fourier transform interferometer. The rotational analysis of the symmetric out-of-plane C-H bend 22(1)0 fundamental band at 722.132993(5) cm-1 was performed, allowing 6760 lines to be assigned. These lines were fitted simultaneously to literature data on nu1 [A. Mellouki, R. Georges, M. Herman, D. L. Snavely, and S. Leytner, Chem. Phys. 220, 311-322 (1997)] and microwave lines [G. Wlodarczak, L. Martinache, J. Demaison, and B. P. Van Eijck, J. Mol. Spectrosc. 127, 200-208 (1988)]. A set of rotation parameters was determined for the ground state in Ir and IIIr representations, together with vibration-rotation constants for the v1 = 1 and v22 = 1 vibrational states. The fine structure in the strongest of the hot bands in that range was highlighted by division, from the experimental data, of the spectrum of the 22(1)0 band, computed using the vibration-rotation parameters. The rotational assignment of 930 lines in the strongest hot band was performed. The 22(1)024(1)1 vibrational assignment is proposed, leading to x22,24 = 1.90 cm-1. The transition dipole matrix element for the 22(1)0 band is estimated to || || = 2 x 10(-4) D. Copyright 1999 Academic Press.     

High-Resolution Infrared Spectrum of nu5, nu4, nu3, nu4 + nu5, and 2nu4 Band Systems of Deuterobromoacetylene

High-resolution vibration-rotation spectra of gas-phase deuterobromoacetylene have been recorded in the 240-990 cm-1 infrared region. The analyzed band systems are rich in hot bands and have a high density of lines. Five band systems and a total of 124 vibration-rotation bands of the isotopic species DCC79Br and DCC81Br have been rotationally analyzed. Accurate rotational parameters and vibrational wavenumbers for 33 vibrational states of each species have been obtained from the rotational analysis. l doubling and rotational l resonance have been observed on some states and the respective resonance parameters have been obtained through nonlinear least-squares optimization. A Fermi resonance block model with perturbation terms has been used for the analysis of the vibrational states. With optimized parameters, the model produces root-mean-square deviations of observed - calculated wavenumbers of about 0.3 cm-1 for both isotopic species. Copyright 1999 Academic Press.     

Hyperinsulinemia is associated with the incidence of hypertension and dyslipidemia in middle-aged men

In addition to the previously observed band system nu6 + (n + 1)nu9-nnu9 with n = 0 to 7, Deltal = 0, and l = n near 611 cm-1, we have identified the nu6 + (n + 1)nu9 - (n + 2)nu9 system with n = 0 to 6, Deltal = 0, and l = n + 2 near 397 cm-1. From these bands the rovibrational levels of the states (v6, nv9) with n < 4 have been determined and spectroscopic parameters have been obtained taking into account rotational and vibrational l-type resonances. Effective anharmonicity constants x69 and g69 have been calculated also for levels with n >/= 4. Copyright 1998 Academic Press.     

Positions and Intensities in the 2nu4/nu1/nu3 Vibrational System of 14NH3 Near 3 μm

Line positions and line intensities of the nu1, nu3, and 2nu4 bands of 14NH3 were analyzed using line positions from 0.0054 cm-1 apodized resolution FT spectra recorded at Orsay and using line intensities from 0.011 cm-1 unapodized resolution FT spectra recorded at Kitt Peak National Observatory. About 2110 lines with J' 相似文献   

The binding sites of quinones in photosynthetic bacterial reaction centers investigated by light-induced FTIR difference spectroscopy: assignment of the QA vibrations in Rhodobacter sphaeroides using 18O- or 13C-labeled ubiquinone and vitamin K1

Light-induced FTIR difference spectra of the photoreduction of the primary quinone acceptor QA have been obtained for Rhodobacter sphaeroides RCs reconstituted with a series of isotopically labeled quinones in order to separate the contributions of the quinone from those of the protein. The isotopic shifts observed in the QA-/QA spectra of RCs reconstituted with ubiquinones (Q1, Q6) or vitamin K1 18O-labeled on their carbonyl oxygens and with fully 13C-labeled Q8 lead to a clear identification of the quinone bands from both the neutral and anion forms. Double-difference spectra from pairs of QA-/QA spectra obtained from 18O/16O Q6, 18O/16O Q1, 13C/12C Q8, 13C18O/12C16O Q8, and 18O/16O vitamin K1 allow the C = O modes of QA in vivo to be identified unambiguously for the first time. For all the investigated unlabeled quinones, two carbonyl bands are demasked, at 1660 and 1628 cm-1 for neutral ubiquinones and at 1651 and 1640 cm-1 for vitamin K1, while C = C bands are found at 1608 and 1588 cm-1 for vitamin K1 and at 1601 cm-1 for ubiquinones. Compared with the spectra of the isolated quinones, the generally smaller width observed for the C = O and C = C bands in vivo suggests precise interactions between the quinone and the contours of the protein at a single, well-defined QA site. The different frequency downshifts of the two C = O bands upon binding to the QA site underscore the inequivalence of the two carbonyls in providing asymmetrical bonding interactions with the protein. The comparison of the isotopic shifts observed for the various quinone C = O and C = C bands in vitro and in vivo demonstrates that the admixture of C = O and C = C characters in these modes is strongly affected by the binding of QA to its anchoring site. In particular, the bands at 1628 and 1601 cm-1 of Q6 in vivo exhibit highly mixed C = O and C = C characters. In contrast, the methoxy groups of the ubiquinones do not appear to suffer large strain upon binding. The closeness of the QA-/QA spectra for Q1 and Q6 indicates that a possible role of the chain in providing the proper positioning of the quinone ring in the site for both the oxidized and reduced states of QA cannot extend significantly beyond the first isoprene unit.(ABSTRACT TRUNCATED AT 400 WORDS)     

ATP-Induced phosphorylation of the sarcoplasmic reticulum Ca2+ ATPase: molecular interpretation of infrared difference spectra

Time-resolved infrared difference spectra of the ATP-induced phosphorylation of the sarcoplasmic reticulum Ca2+-ATPase have been recorded in H2O and 2H2O at pH 7.0 and 1 degrees C. The reaction was induced by ATP release from P3-1-(2-nitro)phenylethyladenosine 5'-triphosphate (caged ATP) and from [gamma-18O3]caged ATP. A band at 1546 cm-1, not observed with the deuterated enzyme, can be assigned to the amide II mode of the protein backbone and indicates that a conformational change associated with ATPase phosphorylation takes place after ATP binding. This is also indicated between 1700 and 1610 cm-1, where bandshifts of up to 10 cm-1 observed upon protein deuteration suggest that amide I modes of the protein backbone dominate the difference spectrum. From the band positions it is deduced that alpha-helical, beta-sheet, and probably beta-turn structures are affected in the phosphorylation reaction. Model spectra of acetyl phosphate, acetate, ATP, and ADP suggest the tentative assignment of some of the bands of the phosphorylation spectrum to the molecular groups of ATP and Asp351, which participate directly in the phosphate transfer reaction: a positive band at 1719 cm-1 to the C==O group of aspartyl phosphate, a negative band at 1239 cm-1 to the nuas(PO2-) modes of the bound ATP molecule, and a positive band at 1131 cm-1 to the nuas(PO32-) mode of the phosphoenzyme phosphate group, the latter assignment being supported by the band's sensitivity toward isotopic substitution in the gamma-phosphate of ATP. Band positions and shapes of these bands indicate that the alpha- and/or beta-phosphate(s) of the bound ATP molecule become partly dehydrated when ATP binds to the ATPase, that the phosphoenzyme phosphate group is unprotonated at pH 7.0, and that the C==O group of aspartyl phosphate does not interact with bulk water. The Ca2+ binding sites seem to be largely undisturbed by the phosphorylation reaction, and a functional role of the side chains of Asn, Gln, and Arg residues was not detected.