PubMed Health⌕ Search

Biomedical subjects

Robert Berger

Publications and source records attributed to Robert Berger.

14 recordsLinked to original sources
PubMed2006

Pseudotetrahedral polyhalocubanes: synthesis, structures, and parity violating energy differences.

All possible pseudotetrahedral, stable polyhalocubanes were prepared, and their structures were proven by NMR spectroscopy and X-ray crystallography. Parity violating energy differences (DeltaEpv) and vibrational frequency shifts were computed. The DeltaEpv values are predicted to be one to two orders of magnitude smaller than those for the corresponding polyhalomethanes. However, the DeltaEpv energy ordering is the same as that for the methane analogues. For both substance classes, the (S) isomers are, with the exception of the bromochlorofluoroiodo derivatives, more stable than the (R) forms.

Journal Article↗
PubMed2006

Doubly protonated benzene in the gas phase.

Structural aspects and the unimolecular fragmentations of doubly protonated benzene are studied by means of tandem-mass spectrometry. The corresponding dications are generated by electron ionization (EI) of 1,3- and 1,4-cyclohexadienes, respectively. It is suggested that EI of 1,3-cyclohexadiene leads to the singlet state of doubly protonated benzene, whereas EI of 1,4-cyclohexadiene yields a mixture of singlet and triplet states. Unimolecular fragmentation of doubly protonated benzene exclusively proceeds via dehydrogenation leading to the benzene dication. The proton affinities (PAs) of protonated benzene amount to PA(C(6)H(7)(+))(meta) = 1.9 +/- 0.3 eV for protonation taking place at the meta-position, PA(C(6)H(7)(+))(ortho) = 1.5 +/- 0.2 eV, and PA(C(6)H(7)(+))(para) = 0.9 +/- 0.2 eV, respectively. Various facets of the experiments are compared with density functional theory calculations and generally good agreement is found.

Journal Article↗
PubMed2005

Density functional calculations of molecular parity-violating effects within the zeroth-order regular approximation.

A (quasirelativistic) two-component density functional theory (DFT) approach to the computation of parity-violating energy differences between enantiomers is presented which is based on the zeroth-order regular approximation (ZORA). This approach is employed herein to compute parity-violating energy differences between several P and M conformations of dihydrogen dichalcogenides (H2X2 with X=O, S, Se, Te, Po), of which some compounds have recently been suggested as potential molecular candidates for the first experimental measurement of parity-violating effects in chiral molecules. The DFT ZORA results obtained in this work with "pure" density functionals are anticipated to deviate by well less than 1% from data that would be computed within related (relativistic) four-component Dirac-Kohn-Sham-Coulomb schemes. In our implementation of the ZORA slightly larger relative deviations are expected for hybrid functionals, depending on the amount of "exact" exchange. For B3LYP (20% exact exchange) differences are estimated to amount to at most 3% in hydrogen peroxide, 2% in disulfane, and 1% or less for the heavier homologs. Thus, the present two-component approach is expected to perform excellently when compared to four-component density functional schemes while being at the same time computationally more efficient. The ZORA approach will therefore be of particular interest for the prediction of parity-violating vibrational frequency shifts, for instance, in isotopomers of H(2)Se(2) and H(2)Te(2).

Journal Article↗
PubMed2005

Revision of the second ionization energy of toluene.

Charge stripping (CS) of the molecular ion of toluene, C(7)H(8) (+)-->C(7)H(8) (2+)+e, is often used as a reference for the determination of second ionization energies in energy-resolved CS experiments. For calibration of the kinetic energy scale, a value of IE(C(7)H(8) (+))=(15.7+/-0.2) eV derived from the appearance energy of the toluene dication upon electron ionization has been accepted generally. Triggered by some recent discrepancies between CS measurements on the one hand and different experimental methods as well as theoretical predictions on the other, we have reinvestigated the photon-induced double ionization of toluene using synchrotron radiation. These photoionization measurements yield phenomenological appearance energies of AE(C(7)H(8) (+))=(8.81+/-0.03) eV for the monocation and AE(C(7)H(8) (2+))=(23.81+/-0.06) eV for the dication. The former is in good agreement with a much more precise spectroscopic value, IE(C(7)H(8))=(8.8276+/-0.0006) eV. Explicit consideration of the Franck-Condon envelopes associated with photoionization to the dication in conjunction with the application of the Wannier law leads to an adiabatic ionization energy IE(a)(C(7)H(8) (+))=(14.8+/-0.1) eV, which is as much as 0.9 eV lower than the previous value derived from electron ionization. Because in many previous CS measurements the transition C(7)H(8) (+)-->C(7)H(8) (2+)+e was used as a reference, the energetics of several gaseous dications might need some readjustment.

Journal Article↗
PubMed2005

Short-term outcomes with small intestinal submucosa for ventral abdominal hernia.

HYPOTHESIS: A bioabsorbable tissue scaffold of porcine submucosal small intestine extracellular matrix (Surgisis Gold [SIS]; Cook Biotech Inc, West Lafayette, Ind) mesh is safe and effective for ventral hernia repair. DESIGN: Retrospective case series at a university teaching hospital. PATIENTS: Fifty-three consecutive patients having 8-ply SIS mesh repair of ventral abdominal hernias. MAIN OUTCOME MEASURES: Early complications, reoperation, hernia recurrence, mesh or wound infection, or reaction. Outcomes reported and compared on an intention-to-treat basis. RESULTS: Patients were stratified by wound class: clean, clean-contaminated and contaminated, or dirty. Median follow-up was 14 months (range, 2-29 months) during which there were 22 complications (41%), 17 early reoperations (32%), 13 partial dehiscences (21%), 6 mesh reactions (11%), and 9 recurrent hernias (17%). Seven recurrent hernias (78%) in critically ill, patients with dirty wounds had the SIS mesh removed owing to infection or reoperation. In patients without SIS mesh removal or debridement, 1 (2.2%) of 44 developed a recurrent hernia at 6 months. Patients with dirty wounds were more likely to need early reoperation (P<.001), develop a complication (P<.01), partial wound dehiscence (P<.05), or recurrent hernia (P<.01) compared with patients with clean wounds. Critically ill patients were more likely to have hernia recurrence (P<.05), early reoperation (P<.001), and postoperative complications (P<.05). CONCLUSIONS: Eight-ply SIS mesh is safe in clean and clean-contaminated hernia repair with satisfactory short-term outcomes. However, delayed wound infection, repeated operation, and mesh debridement warrant cautious use of SIS mesh in critically ill patients and those with dirty wounds.

Critical Illness↗
PubMed2004

Ion chemistry of OV(OCH3)3 in the gas phase: molecular cations and anions and their primary fragmentations.

Trimethyl vanadate(V), OV(OCH(3))(3) (1), is examined by various mass spectrometric means. Photoionization experiments yield an ionization energy of IE(OV(OCH(3))(3)) = 9.54 +/- 0.05 eV for the neutral molecule. The primary fragmentation of the molecular cation 1(+), i.e., loss of neutral formaldehyde, can occur via two independent routes of hydrogen migrations to afford the formal V(IV) compounds HOV(OCH(3))(2)(+) and OV(OCH(3))(CH(3)OH)(+), respectively. These two pathways are associated with low-lying activation barriers of almost identical height. At elevated energies, direct V-O bond cleavage of 1(+) allows for expulsion of a methoxy radical concomitant with the generation of the cationic fragment OV(OCH(3))(2)(+), a formal V(V) compound. Trimethyl vanadate can also form a molecular anion, 1(-), whose most abundant dissociation channel involves loss of a methyl radical, thereby leading to the formal V(V) compound OV(OCH(3))(2)O(-). Various mass spectrometric experiments and extensive theoretical studies provide detailed insight into the ion structures and the relative energetics of the primary dissociation reactions of the molecular cations and anions of 1.

Journal Article↗
PubMed2003

The role of robotic surgery in morbid obesity.

The purpose of this review was to form a collaborative opinion regarding the utility of robotic technology, specifically the da Vinci robot (Intuitive Surgical, Inc., Sunnyvale, CA), for bariatric surgery. Eleven surgeons are currently using the da Vinci system to perform laparoscopic bariatric surgery. The surgeons were queried about the type of robotic bariatric surgery and number of cases performed, complications, and any available outcomes data. They were also asked to give their opinion of the current state of robotic bariatric surgery. Ten of the 11 surgeons responded. Six surgeons are currently using the system for Roux-en-Y gastric bypass, three for laparoscopic adjustable gastric banding, and three for biliary pancreatic diversion. Robotic technology is successfully being applied to bariatric surgery in a few advanced minimally invasive surgery centers throughout the United States.

Gastric Bypass↗
PubMed2002

Power of outcome measurements to detect clinically significant changes in pulmonary rehabilitation of patients with COPD.

STUDY OBJECTIVES: Several validated instruments are used to measure outcomes, such as exercise performance, dyspnea, and health-related quality of life after pulmonary rehabilitation (PR) in patients with COPD. However, no study has simultaneously compared the responsiveness of the most frequently used outcome measurements after PR. We designed this study to investigate the capacity of several of the most frequently used outcome measurements to detect changes after PR in a population of patients with severe COPD who qualified for lung volume reduction surgery. DESIGN, PATIENTS, AND INTERVENTIONS: We evaluated 37 patients with severe COPD (FEV(1) < 40%) before and after 6 to 8 weeks of outpatient PR. The following frequently used tools were evaluated: the 6-min walk distance (6MWD); functional dyspnea with the Medical Research Council (MRC) scale; baseline and transitional dyspnea index (BDI/TDI); resting and 6MWD visual analog scale (VAS); quality of life with a generic tool (the Short Form-36 [SF-36]); and two disease-specific tools, the Chronic Respiratory Disease Questionnaire (CRQ) and the St. George's Respiratory Questionnaire (SGRQ). RESULTS: After PR, mean +/- SD 6MWD increased in 33 of 37 patients (89%), from 285 +/- 97 to 343 +/- 92 m (p = 0.009). Improvements were seen also in the MRC scale in 23 of 37 patients (62%; from 2.27 +/- 0.8 to 1.86 +/- 0.6; p = 0.01); in CRQ dyspnea in 25 of 37 patients (67%; from 3.25 +/- 0.9 to 3.90 +/- 1.4; p = 0.02); in CRQ mastery in 22 of 37 patients (60%; from 4.37 +/- 1.4 to 5.14 +/- 1.3; p = 0.01); and in BDI/TDI functional in 24 of 37 patients (64%; from 1.4 +/- 0.8 to 0.7 +/- 1.1; p = 0.002). There were smaller improvements in the SGRQ in 18 of 37 patients (48%) and in the SF-36 in 19 of 37 patients (51%), but they were not statistically significant. There were good correlations between the dyspnea components of all the tools. The 6MWD change did not correlate with the changes in the other outcomes. Clinically significant changes in the values for those outcome tools were detected in > 50% of patients for the BDI/TDI, 29% of patients for the MRC scale, in 37% of patients for the 6MWD, in 48% of patients for the VAS at peak exercise, in > 50% of patients for the CRQ, and in 40% of patients for the SGRQ. CONCLUSIONS: We conclude that the VAS peak exercise, BDI/TDI, and CRQ adequately reflect the beneficial effects of PR. The 6MWD evaluates a unique domain not related to quality of life. Due to their simplicity and sensitivity, VAS at peak exercise, 6MWD, and CRQ may be the best practical tools to evaluate responsiveness to PR.

Aged↗