Positive and negative signal and line shape in stimulated Raman spectroscopy: Resonance femtosecond Raman spectra of diphenylbutadiene.

Resonance stimulated Raman signal and line shape are evaluated analytically under common electronic/vibrational dephasing and exponential Raman/probe pulse, exp(-|t|/τ). Generally, the signal from a particular state includes contributions from higher and lower electronic states. Thus, with S0 → S1 actinic excitation, the Raman signal consists of 15 Feynman diagrams entering with different signs. The negative sign indicates vibrational coherences in S1 or higher Sn, whereas the positive sign reveals coherences in S0 or Sn via S1 → Sn → Sm (n < m) coupling. The signal complexity is in contrast to spontaneous Raman with its single diagram only. The results are applied to femtosecond stimulated Raman spectra of trans-trans, cis-trans (ct), and cis-cis (cc) 1,4-diphenyl-1,3-butadiene, the ct and cc being reported for the first time. Upon actinic excitation, the Stokes spectra show negative bands from S1 or Sn. When approaching higher resonances Sn → Sm, some Raman bands switch their sign from negative to positive, thus, indicating new coherences in Sn. The results are discussed, and the measured Raman spectra are compared to the computed quantum-chemical spectra.

An unusual cause for globus sensation: infected tracheal diverticulum with abscess formation.

CASE REPORT: A 43-year-old woman presented with a 3-week history of globus sensation and malaise. A computed tomography scan of her neck showed a large right paratracheal abscess secondary to an infected tracheal diverticulum. The patient was admitted under the ENT surgical team, and underwent incision and drainage of the abscess. There were no post-operative complications and she was discharged home after 2 days, on oral antibiotics. CONCLUSION: This case demonstrates that a tracheal diverticulum may become infected and present as a cervical abscess. To our knowledge, this is the fourth reported case in the international literature of abscess formation related to an infected tracheal diverticulum.

Substitution pattern dependent behavior of the singlet excited states in symmetrically fluorinated biphenyls.

Biphenyls are important basic chromophore systems that offer a possibility to study the effects of chemical substitution on the lower-lying excited states without complications from photoisomerization or other side processes. For several symmetric biphenyls, pristine biphenyl (bP0), 4,4'-difluorobiphenyl (bP2), 2,3,5,6,2',3',5',6'-octafluorobiphenyl (bP8), and perfluorobiphenyl (bP10), we report stationary and ultrafast solution-phase spectra rationalized with the aid of computations by means of the XMCQDPT2 multi-configuration perturbation theory and TDDFT. Polyfluorination tends to broaden the gap between the nearly degenerate S1 + S2 pair of states and the S3 state in bP8 and bP10, yet relaxation from any sheet of the S1-S3 manifold leads through a system of state crossings to the same stationary points in S1. Unlike bP0 and bP2 where the relaxed excited state is planar and non-polar, excited bP8 and bP10 exhibit sudden polarization to give a symmetry-lowered excited state via pseudo-Jahn-Teller interactions involving S1 and S2. Of particular interest is excited bP10 which reveals both sudden polarization and loss of planarity of one phenyl ring. We also demonstrate the unsatisfactory performance of the TDDFT methodology as applied to the biphenyls.

On the intersystem crossing rate in a Platinum(II) donor-bridge-acceptor triad.

The rates of ultrafast intersystem crossing in acceptor-bridge-donor molecules centered on Pt(II) acetylides are investigated. Specifically, a Pt(II) trans-acetylide triad NAP--Pt--Ph-CH2-PTZ [1], with acceptor 4-ethynyl-N-octyl-1,8-naphthalimide (NAP) and donor phenothiazine (PTZ), is examined in detail. We have previously shown that optical excitation in [1] leads to a manifold of singlet charge-transfer states, S*, which evolve via a triplet charge-transfer manifold into a triplet state 3NAP centered on the acceptor ligand and partly to a charge-separated state 3CSS (NAP--Pt-PTZ+). A complex cascade of electron transfer processes was observed, but intersystem crossing (ISC) rates were not explicitly resolved due to lack of spin selectivity of most ultrafast spectroscopies. Here we revisit the question of ISC with a combination and complementary analysis of (i) transient absorption, (ii) ultrafast broadband fluorescence upconversion, FLUP, which is only sensitive to emissive states, and (iii) femtosecond stimulated Raman spectroscopy, FSR. Raman resonance conditions allow us to observe S* and 3NAP exclusively by FSR, through vibrations which are pertinent only to these two states. This combination of methods enabled us to extract the intersystem crossing rates that were not previously accessible. Multiple timescales (1.6 ps to ∼20 ps) are associated with the rise of triplet species, which can now be assigned conclusively to multiple ISC pathways from a manifold of hot charge-transfer singlet states. The analysis is consistent with previous transient infrared spectroscopy data. A similar rate of ISC, up to 20 ps, is observed in the trans-acetylide NAP--Pt--Ph [2] which maintains two acetylide groups across the platinum center but lacks a donor unit, whilst removal of one acetylide group in mono-acetylide NAP--Pt-Cl [3] leads to >10-fold deceleration of the intersystem crossing process. Our work provides insight on the intersystem crossing dynamics of the organo-metallic complexes, and identifies a general method based on complementary ultrafast spectroscopies to disentangle complex spin, electronic and vibrational processes following photoexcitation.

Photoisomerization dynamics of trans-trans, cis-trans, and cis-cis diphenylbutadiene from broadband transient absorption spectroscopy and calculations.

The photoisomerization path and dynamics of trans-trans (ttD), cis-trans (ctD), and cis-cis (ccD) 1,4-diphenyl-1,3-butadiene (DPB) in solution are studied with broadband transient absorption (TA) spectroscopy and quantum chemical calculations. For ttD in n-hexane, 2-photon-excited TA spectra indicate that the 2Ag state is located above 1-photon allowed 1Bu (S1) by ∼1000 cm-1. Following S0 → S1 optical excitation, the isomerization occurs via torsion about a butadiene double bond to perpendicular molecular configuration P. The P-state is detected in ccD with an excited-state absorption band at 390 nm. This P-band develops during S1 → P half-torsion with time of 0.15 ps, followed further by P → S0 half-torsion and simultaneous decay with 1.6 ps in acetonitrile and 5 ps in n-hexane. In addition, two oscillation cycles between P and S1 population are observed before equilibration in n-hexane. For ctD, an indication of rising and decaying P is found in acetonitrile. The vast majority of ctD species photoisomerizes to ttD and not to ccD, in agreement a with calculated low torsional barrier about the cis double bond and high barrier about the trans double bond. Photoisomerization yield Y and time τi depend drastically on the solvent polarity. Thus, in n-hexane, the isomerization ttD → ctD has yield Ytt,ct = 0.1 and time τi = 829 ps, while in acetonitrile, Ytt,ct = 0.4 and τi = 27 ps. The 30-fold acceleration of the isomerization in acetonitrile clearly reflects a highly polar character of P, consistent with a dipole moment µP > 9.6 D. The results for DPB are discussed in comparison to stilbene.

Transient Rotamerism and Photoisomerization Dynamics of trans- and cis-Naphthylstilbene.

The rotamerism and photoisomerization of trans- and cis-1,2-di-(2-naphthyl)ethylene (tN and cN) are studied with stationary and transient absorption spectroscopies assisted by quantum chemical calculations. Absorption and emission spectra of rotamers (rotational isomers) tN-S (C2h-symmetric), tN-A (C1), and tN-S' (C2) are derived with a 53:47 ratio of tN-S to tN-A. Upon photoexcitation, the equilibration of the rotamers in S0 (rotamerization) is observed in the bleach region with characteristic time τrotamer ≈ 0.5 ns. With excitation at 364 nm, the S0 equilibrium shifts because, mainly, tN-A is bleached and the rotamerization becomes traceable, whereas with excitation at 345 nm, the equilibrium is preserved and the bleach spectrum remains unchanged. It is just long-lived (∼2 ns) S1 that allows for monitoring the rotamer dynamics in S0. Replacement of the stilbene phenyl rings with larger naphthyls increases the S1 → P torsional barrier E1act toward perpendicular configuration P both from cis and trans configurations. In tN, the radiative relaxation with τR ≈ 3.7 ns becomes the main deactivation channel, and accordingly, the measured decays show nearly no dependence on the solvent viscosity. The cis-to-trans photoisomerization occurs via two paths: adiabatic cS1 → P → tS1 (20%) and more common nonadiabatic cS1 → P → S0 (80%). The barrier cS1 → P in the cis-isomer is reduced in polar solvents because of a zwitterionic character of P. The P-state is directly detected with the cN isomer in acetonitrile by an excited-state absorption band at 400 nm developing with 0.7 ps and decaying with 1.6 ps. Two dihydrophenanthrene (DHP)-like products result from photoexcited cN. The metastable DHP-A builds up transiently from cN-A, and its spectrum at about 550 nm matches the published DHP absorption. The stable DHP-S' accumulates under stationary illumination and is formed either from excited cN-S' or metastable DHP-A.

Gamma Ray Glow Observations at 20-km Altitude.

In the spring of 2017 an ER-2 aircraft campaign was undertaken over continental United States to observe energetic radiation from thunderstorms and lightning. The payload consisted of a suite of instruments designed to detect optical signals, electric fields, and gamma rays from lightning. Starting from Georgia, USA, 16 flights were performed, for a total of about 70 flight hours at a cruise altitude of 20 km. Of these, 45 flight hours were over thunderstorm regions. An analysis of two gamma ray glow events that were observed over Colorado at 21:47 UT on 8 May 2017 is presented. We explore the charge structure of the cloud system, as well as possible mechanisms that can produce the gamma ray glows. The thundercloud system we passed during the gamma ray glow observation had strong convection in the core of the cloud system. Electric field measurements combined with radar and radio measurements suggest an inverted charge structure, with an upper negative charge layer and a lower positive charge layer. Based on modeling results, we were not able to unambiguously determine the production mechanism. Possible mechanisms are either an enhancement of cosmic background locally (above or below 20 km) by an electric field below the local threshold or an enhancement of the cosmic background inside the cloud but then with normal polarity and an electric field well above the Relativistic Runaway Electron Avalanche threshold.

Epidemiological survey of echinococcosis in Tibet Autonomous Region of China.

BACKGROUND: The echinococcosis is prevalent in 10 provinces /autonomous region in western and northern China. Epidemiological survey of echinococcosis in China in 2012 showed the average prevalence of four counties in Tibet Autonomous Region (TAR) is 4.23%, much higher than the average prevalence in China (0.24%). It is important to understand the transmission risks and the prevalence of echinococcosis in human and animals in TAR. METHODS: A stratified and proportionate sampling method was used to select samples in TAR. The selected residents were examined by B-ultrasonography diagnostic, and the faeces of dogs were tested for the canine coproantigen against Echinococcus spp. using enzyme-linked immunosorbent assay. The internal organs of slaughtered domestic animals were examined by visual examination and palpation. The awareness of the prevention and control of echinococcosis among of residents and students was investigated using questionnaire. All data were inputted using double entry in the Epi Info database, with error correction by double-entry comparison, the statistical analysis of all data was processed using SPSS 21.0, and the map was mapped using ArcGIS 10.1, the data was tested by Chi-square test and Cochran-Armitage trend test. RESULTS: A total of 80 384 people, 7564 faeces of dogs, and 2103 internal organs of slaughtered domestic animals were examined. The prevalence of echinococcosis in humans in TAR was 1.66%, the positive rate in females (1.92%) was significantly higher than that in males (1.41%), (χ2 = 30.31, P < 0.01), the positive rate of echinococcosis was positively associated with age (χ2trend = 423.95, P < 0.01), and the occupational populations with high positive rates of echinococcosis were herdsmen (3.66%) and monks (3.48%). The average positive rate of Echinococcus coproantigen in TAR was 7.30%. The positive rate of echinococcosis in livestock for the whole region was 11.84%. The average awareness rate of echinococcosis across the region was 33.39%. CONCLUSIONS: A high prevalence of echinococcosis is found across the TAR, representing a very serious concern to human health. Efforts should be made to develop an action plan for echinococcosis prevention and control as soon as possible, so as to control the endemic of echinococcosis and reduce the medical burden on the population.

Staphylococcus aureus in the nose and throat of Iowan families.

The study objective was to determine the prevalence of Staphylococcus aureus colonisation in the nares and oropharynx of healthy persons and identify any risk factors associated with such S. aureus colonisation. In total 263 participants (177 adults and 86 minors) comprising 95 families were enrolled in a year-long prospective cohort study from one urban and one rural county in eastern Iowa, USA, through local newspaper advertisements and email lists and through the Keokuk Rural Health Study. Potential risk factors including demographic factors, medical history, farming and healthcare exposure were assessed. Among the participants, 25.4% of adults and 36.1% minors carried S. aureus in their nares and 37.9% of adults carried it in their oropharynx. The overall prevalence was 44.1% among adults and 36.1% for minors. Having at least one positive environmental site for S. aureus in the family home was associated with colonisation (prevalence ratio: 1.34, 95% CI: 1.07-1.66). The sensitivity of the oropharyngeal cultures was greater than that of the nares cultures (86.1% compared with 58.2%, respectively). In conclusion, the nares and oropharynx are both important colonisation sites for healthy community members and the presence of S. aureus in the home environment is associated with an increased probability of colonisation.

Characterization of Disulfide Linkages in Proteins by 193 nm Ultraviolet Photodissociation (UVPD) Mass Spectrometry.

Deciphering disulfide bond patterns in proteins remains a significant challenge. In the present study, interlinked disulfide bonds connecting peptide chains are homolytically cleaved with 193 nm ultraviolet photodissociation (UVPD). Analysis of insulin showcased the ability of UVPD to cleave multiple disulfide bonds and provide sequence coverage of the peptide chains in the same MS/MS event. For proteins containing more complex disulfide bonding patterns, an approach combining partial reduction and alkylation mitigated disulfide scrambling and allowed assignment of the array of disulfide bonds. The 4 disulfide bonds of lysozyme and the 19 disulfide bonds of serotransferrin were characterized through LC/UVPD-MS analysis of nonreduced and partially reduced protein digests.

Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.

Photoisomerization of 2,2'-, 3,3'-, and 4,4'-difluorostilbene (F2, F3, F4, respectively) in n-hexane, perfluoro-n-hexane, and acetonitrile is studied with broadband transient absorption (TA) and femtosecond stimulated Raman (FSR) spectroscopy and by DFT/TDDFT calculations. F2 and F3 possess three rotamers (rotational isomers) each, while F4 has one single conformation only. These differences are reflected in TA and FSR spectra. Thus F4 reveals a monoexponential decay of TA with τ1 = 172 ps in n-hexane, as expected for a single species. For F2 and F3, the decays are biexponential in all solvents, corresponding to two distinctly discerned rotamers or rotamer fractions. Specifically, for F2 in n-hexane, τ1 = 357 ps (83%) and τ2 = 62 ps (17%), and for F3 in the same solvent, τ1 = 222 ps (57%), and τ2 = 81 ps (43%). The weights in brackets agree with theoretically estimated ground-state abundances of the rotamers. Furthermore, a global fit of the TA and FSR data allows us to extract the spectra of the pure rotamers. The Raman spectra of S0 and S1 are in qualitative agreement with calculations.

SITS Derivatization of Peptides to Enhance 266 nm Ultraviolet Photodissociation (UVPD).

N-terminal derivatization of peptides with the chromogenic reagent 4-acetamido-4-isothiocyanatostilbene-2,2-disulfonic acid (SITS) is demonstrated to enhance the efficiency of 266 nm ultraviolet photodissociation (UVPD). Attachment of the chromophore results in a mass shift of 454 Da and provides significant gains in the number and abundances of diagnostic fragment ions upon UVPD. Activation of SITS-tagged peptides with 266 nm UVPD leads to many fragment ions akin to the a/b/y ions commonly produced by CID, along with other sequence ions (c, x, and z) typically accessed through higher energy pathways. Extreme bias towards C-terminal fragment ions is observed upon activation of SITS-tagged peptides using multiple 266 nm laser pulses. Due to the high reaction efficiency of the isothiocyanate coupling to the N-terminus of peptides, we demonstrate the ability to adapt this strategy to a high-throughput LC-MS/MS workflow with 266 nm UVPD. Graphical Abstract ᅟ.

Acid-catalysed thermal cycloreversion of a diarylethene: a potential way for triggered release of stored light energy?

Upon addition of catalytic amounts of acid, a closed diarylethene derivative carrying a fluorenol moiety undergoes facile thermal ring opening. The underlying thermodynamics and kinetics of the entire system have been analysed experimentally as well as computationally. Our work suggests that general acid catalysis provides a useful tool to bypass thermal barriers, by opening new reaction pathways, and to efficiently trigger the release of light energy stored in photoswitches.

Photoisomerization pathways and Raman activity of 1,1'-difluorostilbene.

The photoisomerization of 1,1'-difluorostilbene, following S0→S1 optical excitation in solution, was studied with femtosecond broadband transient absorption and stimulated Raman spectroscopy, and by quantum-chemical calculations. In n-hexane, trans-to-cis (t→c) isomerization starts with Franck-Condon relaxation (τ1t = 0.07 ps) followed by nearly barrierless torsion around the ethylenic bond (τ2t ≈ 0.3 ps) to a perpendicular conformation P. About 50% of the excited molecules are trapped in P, while others reach the S1(cis) conformation adiabatically. For the opposite cis-to-trans (c→t) path, the dynamics in n-hexane (τ1c = 0.04 ps, τ2c = 0.7 ps) suggest a 5 kJ/mol barrier between the relaxed S1(cis) and P states. The subsequent P decay with τ3 = 0.4 ps is followed by much slower ground-state recovery (τ4 ≈ 3 ps), indicating an intermediate state X. The t→P and c→P torsion depend on solvent viscosity and polarity, whereas the P→X→S0 relaxation and residual torsion is viscosity-independent but still polarity-dependent. Photoisomerization yields are derived from the transient absorption data and compared to those from actinometric measurements. Low-frequency oscillations in the transient signal are assigned to nuclei motions. Transient and stationary stimulated Raman spectra are compared to calculations. Early Franck-Condon Raman spectra differ from those of the quasistationary trans or cis S1 state. The photoisomerization behavior of stilbene and vinyl-substituted derivatives is compared and the general features are discussed.

Dual-fluorescence pH probe for bio-labelling.

Although seminaphtorhodafluor (SNARF) dyes are already widely used to measure pH in cells and at biofilms, their synthesis has low yield and results in an unspecific position of a carboxy-group. The separation of 5'- and 6'-carboxy-SNARF reveals a pKa difference of 0.15, calling into question pH measurements with the (commercially available) mixture. Here we replace the bulky external dicarboxyphenyl ring with a propionate group and evaluate the spectral properties of the new derivative. Proceeding to the ethyl-iodoacetamide, covalent linkage to cysteine protein sites is achieved efficiently as shown with a cyanobacterial phytochrome, extending the scarce application of SNARF in bio-labelling in the current literature. Application in fluorescence lifetime imaging is demonstrated both with the lifetime-based and ratiometric-yield method.

A biomechanical investigation of dual growing rods used for fusionless scoliosis correction.

BACKGROUND: The use of dual growing rods is a fusionless surgical approach to the treatment of early onset scoliosis which aims to harness potential growth and correct spinal deformity. The purpose of this study was to compare the in-vitro biomechanical response of two different dual rod designs under axial rotation loading. METHODS: Six porcine spines were dissected into seven level thoracolumbar multi-segment units. Each specimen was mounted and tested in a biaxial Instron machine, undergoing nondestructive left and right axial rotation to peak moments of 4 Nm at a constant rotation rate of 8 deg. s(-1). A motion tracking system (Optotrak) measured 3D displacements of individual vertebrae. Each spine was tested in an un-instrumented state first and then with appropriately sized semi-constrained and 'rigid' growing rods in alternating sequence. The range of motion, neutral zone size and stiffness were calculated from the moment-rotation curves and intervertebral range of motion was calculated from Optotrak data. FINDINGS: Irrespective of test sequence, rigid rods showed a significant reduction of total rotation across all instrumented levels (with increased stiffness) whilst semi-constrained rods exhibited similar rotational behavior to the un-instrumented spines (P<0.05). An 11.1% and 8.0% increase in stiffness for left and right axial rotation respectively and 14.9% reduction in total range of motion were recorded with dual rigid rods compared with semi-constrained rods. INTERPRETATION: Based on these findings, the Semi-constrained growing rods were shown to not increase axial rotation stiffness compared with un-instrumented spines. This is thought to provide a more physiological environment for the growing spine compared to dual rigid rod constructs.

Photoisomerization dynamics and pathways of trans- and cis-azobenzene in solution from broadband femtosecond spectroscopies and calculations.

The photoisomerization of azobenzene in solution was studied experimentally and by calculations. trans-to-cis and cis-to-trans dynamics are described through broadband transient absorption, fluorescence, and stimulated Raman spectroscopy. Transient absorption was extended to cover not only the nπ* band but also the ππ* band in the ultraviolet. Isomerization yields are used for a quantitative comparison of trans and cis transient spectra under different excitation. For the trans-to-cis path upon nπ*(S(1)) excitation, the evolution develops with 0.3, 3, and 16 ps. The first two times reflect population relaxation to a local minimum S(1t )(L) and subsequent transition to a dark intermediate S(1t)(D) over an 8 kJ/mol barrier. The existence of stationary points S(1t)(L) and S(1t)(D) is confirmed by quantum-chemical calculations. The third time corresponds to S(1t) (D) → S0 relaxation to the ground state via an S1/S0 conical intersection over a 12 kJ/mol barrier. Thus, the 16 ps time constant is attributed to the isomerization process and not to vibrational cooling, contrary to the current view and in line with the previous interpretation by Lednev et al. (J. Phys. Chem. 1996, 100, 13338). The decay of the long-lived intermediate S(1t)(D) is consistent with the hula twist rather than with the inversion mechanism. For the cis-totrans reaction following nπ* excitation, signal decay is strongly nonexponential, with 0.1 and 1 ps. The latter (1 ps) is much shorter than the 16 ps decay of the trans isomer, implying different S1/S0 conical intersections and relaxation paths for the cis-totrans and trans-to-cis reaction. New results are also obtained with ππ*(Sn) excitation. Thus, for trans-azobenzene, 50% of the population relaxes to an S1 region, which is not accessible under nπ* excitation. For cis-azobenzene, up to 30% of the excited species isomerize to trans via an Sn/S1 intersection, resulting in a mixed cis/trans S1 population. The isomerization kinetics of azobenzene shows no viscosity dependence, putting into question the torsion mechanism and suggesting the hula-twist isomerization mechanism.

Excited-state Raman spectroscopy with and without actinic excitation: S1 Raman spectra of trans-azobenzene.

We show that femtosecond stimulated Raman spectroscopy can record excited-state spectra in the absence of actinic excitation, if the Raman pump is in resonance with an electronic transition. The approach is illustrated by recording S1 and S0 spectra of trans-azobenzene in n-hexane. The S1 spectra were also measured conventionally, upon nπ* (S0 → S1) actinic excitation. The results are discussed and compared to earlier reports.

Photoisomerization dynamics of stiff-stilbene in solution.

Photoinduced isomerization of 1,1'-bis-indanyliden (stiff-stilbene) in solution was studied with broadband transient absorption and femtosecond Raman spectroscopies, and by quantum-chemical calculations. Trans-to-cis S1 isomerization proceeds over a 600 and 400 cm(-1) barrier in n-hexane and acetonitrile, respectively. The reaction develops on multiple time scales with fast (0.3-0.4 ps) viscosity-independent and slower (2-26 ps) viscosity-dependent components. In the course of intramolecular torsion (which should be the main reaction coordinate) some excited molecules pass through the perpendicular conformation P and reach the cis geometry, to be temporarily trapped there. Subsequently they relax back to P and further to the ground state S0. The cis-to-trans isomerization reveals ultrafast (0.06 ps) oscillatory relaxation followed by 13 ps decay in n-hexane and 2 ps decay in acetonitrile, corresponding to barriers of 800 and 400 cm(-1), respectively. Raman S0 and S1 spectra are reported and discussed. The perpendicular conformation P was not detected, possibly due to its low oscillator strength and short lifetime, or because of strong overlap with hot product spectra. XMCQDPT2 calculations locate a stationary S1 point on the cis side and two perpendicular-pyramidalized stationary points, to be reached from the former over 300 and 680 cm(-1) barrier. Implications for parent stilbene are discussed; in this case we also see evidence for the trans-to-cis adiabatic path, as in stiff-stilbene. Very similar viscosity dependence for the two compounds supports the common isomerization pathway: torsion about the central double bond.