IRMPD Spectroscopy Sheds New (Infrared) Light on the Sulfate Pattern of Carbohydrates.

IR spectroscopy of gas-phase ions is proposed to resolve positional isomers of sulfated carbohydrates. Mass spectrometric fingerprints and gas-phase vibrational spectra in the near and mid-IR regions were obtained for sulfated monosaccharides, yielding unambiguous signatures of sulfated isomers. We report the first systematic exploration of the biologically relevant but notoriously challenging deprotonated state in the near IR region. Remarkably, anions displayed very atypical vibrational profiles, which challenge the well-established DFT (Density Functionnal Theory) modeling. The proposed approach was used to elucidate the sulfate patterns in glycosaminoglycans, a ubiquitous class of mammalian carbohydrates, which is regarded as a major challenge in carbohydrate structural analysis. Isomeric glycosaminoglycan disaccharides from heparin and chondroitin sources were resolved, highlighting the potential of infrared multiple photon dissociation spectroscopy as a novel structural tool for carbohydrates.

Influence of long-range Coulomb interaction in velocity map imaging.

The standard velocity-map imaging (VMI) analysis relies on the simple approximation that the residual Coulomb field experienced by the photoelectron ejected from a neutral or ion system may be neglected. Under this almost universal approximation, the photoelectrons follow ballistic (parabolic) trajectories in the externally applied electric field, and the recorded image may be considered as a 2D projection of the initial photoelectron velocity distribution. There are, however, several circumstances where this approximation is not justified and the influence of long-range forces must absolutely be taken into account for the interpretation and analysis of the recorded images. The aim of this paper is to illustrate this influence by discussing two different situations involving isolated atoms or molecules where the analysis of experimental images cannot be performed without considering long-range Coulomb interactions. The first situation occurs when slow (meV) photoelectrons are photoionized from a neutral system and strongly interact with the attractive Coulomb potential of the residual ion. The result of this interaction is the formation of a more complex structure in the image, as well as the appearance of an intense glory at the center of the image. The second situation, observed also at low energy, occurs in the photodetachment from a multiply charged anion and it is characterized by the presence of a long-range repulsive potential. Then, while the standard VMI approximation is still valid, the very specific features exhibited by the recorded images can be explained only by taking into consideration tunnel detachment through the repulsive Coulomb barrier.

Larvicidal activity of Brazilian plant essential oils against Coenagrionidae larvae.

Odonate larvae can be serious pests that attack fish larvae, postlarvae, and fingerlings in fish culture tanks, causing significant loss in the supply and production of juveniles. This study reports a screen of the essential oils (EOs) of Nectandra megapotamica (Sprengel) Mez, Nectandra grandiflora Nees, Hesperozygis ringens (Bentham) Epling, Ocimum gratissimum L., Aloysia gratissima (Gillies & Hooker) Troncoso, and Lippia sidoides Chamisso against Coenagrionidae larvae. In addition, the most effective EO and its 50% lethal concentration (LC50) and chemical analysis are described. The larvae of Acanthagrion Selys, Homeoura Kennedy, Ischnura Charpentier, and Oxyagrion Selys were used to assess the EO effects. EO obtained from H. ringens, O. gratissimum, and L. sidoides showed the highest larvicidal effects at 19 h of treatment. The major constituents of the EO of H. ringens include pulegone and limonene, while eugenol and Z-beta-ocimene predominate in the EO of O. gratissimum, and carvacrol and rho-cymene were the major compounds of the EO of L. sidoides. Leaf EOs from H. ringens, O. gratissimum, and L. sidoides showed activity against Coenagrionidae larvae at similar concentrations with LC50s of 62.92, 75.05, and 51.65 microl liter(-1), respectively, and these were considered the most promising treatments.

Structural and Energetic Effects of O2'-Ribose Methylation of Protonated Pyrimidine Nucleosides.

The 2'-substituents distinguish DNA from RNA nucleosides. 2'-O-methylation occurs naturally in RNA and plays important roles in biological processes. Such 2'-modifications may alter the hydrogen-bonding interactions of the nucleoside and thus may affect the conformations of the nucleoside in an RNA chain. Structures of the protonated 2'-O-methylated pyrimidine nucleosides were examined by infrared multiple photon dissociation (IRMPD) action spectroscopy, assisted by electronic structure calculations. The glycosidic bond stabilities of the protonated 2'-O-methylated pyrimidine nucleosides, [Nuom+H]+, were also examined and compared to their DNA and RNA nucleoside analogues via energy-resolved collision-induced dissociation (ER-CID). The preferred sites of protonation of the 2'-O-methylated pyrimidine nucleosides parallel their canonical DNA and RNA nucleoside analogues, [dNuo+H]+ and [Nuo+H]+, yet their nucleobase orientation and sugar puckering differ. The glycosidic bond stabilities of the protonated pyrimidine nucleosides follow the order: [dNuo+H]+ < [Nuo+H]+ < [Nuom+H]+. The slightly altered structures help explain the stabilization induced by 2'-O-methylation of the pyrimidine nucleosides.

Analysis of Sulfate Patterns in Glycosaminoglycan Oligosaccharides by MSn Coupled to Infrared Ion Spectroscopy: the Case of GalNAc4S and GalNAc6S.

We report distinctive spectroscopic fingerprints of the monosaccharide standards GalNAc4S and GalNAc6S by coupling mass spectrometry and ion spectroscopy in the 3-µm range. The disaccharide standards CSA and CSC are used to demonstrate the applicability of a novel approach for the analysis of sulfate position in GalNAc-containing glycosaminoglycans. This approach was then used for the analysis of a sample containing CSA and CSC disaccharides. Finally, we discuss the generalization of the coupling of mass spectrometry with ion spectroscopy for the structural analysis of glycosaminoglycans on a tetrasaccharide from dermatan sulfate source. Graphical abstract ᅟ.

Structural and Energetic Effects of O2'-Ribose Methylation of Protonated Purine Nucleosides.

The chemical difference between DNA and RNA nucleosides is their 2'-hydrogen versus 2'-hydroxyl substituents. Modification of the ribosyl moiety at the 2'-position and 2'-O-methylation in particular, is common among natural post-transcriptional modifications of RNA. 2'-Modification may alter the electronic properties and hydrogen-bonding characteristics of the nucleoside and thus may lead to enhanced stabilization or malfunction. The structures and relative glycosidic bond stabilities of the protonated forms of the 2'-O-methylated purine nucleosides, 2'-O-methyladenosine (Adom) and 2'-O-methylguanosine (Guom), were examined using two complementary tandem mass spectrometry approaches, infrared multiple photon dissociation action spectroscopy and energy-resolved collision-induced dissociation. Theoretical calculations were also performed to predict the structures and relative stabilities of stable low-energy conformations of the protonated forms of the 2'-O-methylated purine nucleosides and their infrared spectra in the gas phase. Low-energy conformations highly parallel to those found for the protonated forms of the canonical DNA and RNA purine nucleosides are also found for the protonated 2'-O-methylated purine nucleosides. Importantly, the preferred site of protonation, nucleobase orientation, and sugar puckering are preserved among the DNA, RNA, and 2'-O-methylated variants of the protonated purine nucleosides. The 2'-substituent does however influence hydrogen-bond stabilization as the 2'-O-methyl and 2'-hydroxyl substituents enable a hydrogen-bonding interaction between the 2'- and 3'-substituents, whereas a 2'-hydrogen atom does not. Further, 2'-O-methylation reduces the number of stable low-energy hydrogen-bonded conformations possible and importantly inverts the preferred polarity of this interaction versus that of the RNA analogues. Trends in the CID50% values extracted from survival yield analyses of the 2'-O-methylated and canonical DNA and RNA forms of the protonated purine nucleosides are employed to elucidate their relative glycosidic bond stabilities. The glycosidic bond stability of Adom is found to exceed that of its DNA and RNA analogues. The glycosidic bond stability of Guom is also found to exceed that of its DNA analogue; however, this modification weakens this bond relative to its RNA counterpart. The glycosidic bond stability of the protonated purine nucleosides appears to be correlated with the hydrogen-bond stabilization of the sugar moiety.

Biogenic amines--a possible source for nicotine in mushrooms? A discussion of published literature data.

Mushrooms have, repeatedly, been shown to contain nicotine. Speculation about the source of contamination has been widespread, however the source of nicotine remains unknown. Previous studies indicate that putrescine, an intermediate in nicotine biosynthesis, can be formed in mushrooms, which might be metabolised to form nicotine. Thus, endogenous formation may be a possible cause for elevated nicotine levels in mushrooms. We present evidence from the literature that may support this hypothesis.

Comparison of alpha-ketoisocaproic acid and glucose in rats: effects on insulin and somatostatin release and on islet cAMP content.

The insulinotropic effects of alpha-ketoisocaproic acid and glucose reveal many common characteristics in vivo and in vitro. They qualify as initiators of insulin release, their action is amplified by potentiators of insulin release, and they have a similar potency at equimolar concentrations. The dynamics of insulin release evoked by alpha-ketoisocaproic acid and glucose are similar. Epinephrine completely inhibits the insulinotropic effect of glucose and alpha-ketoisocaproic acid. Mannoheptulose exhibits a complete, immediate and reversible blockade of glucose-induced insulin release. In contrast, inhibition of alpha-ketoisocaproic acid-induced insulin release occurs after a lag period and is not reversed by removal of the inhibitor. alpha-ketoisocaproic acid, at equimolar concentrations, is several-fold more effective than glucose in elevating cAMP content in islet. alpha ketoisocaproic acid and glucose are about equally effective in stimulating somatostatin release from isolated rat pancreatic islets. This stimulation is inhibited by epinephrine. Mannoheptulose inhibits only somatostatin release induced by glucose but not by alpha-ketoisocaproic acid. It suggested that the insulinotropic characteristics of glucose and alpha-ketoisocaproic acid reveal many common features, while their mode of action appears to be different.

Medical comorbidity and schizophrenia: editors' introduction.

Schizophrenia is a heavily biologically determined psychiatric disorder with unequivocal evidence for a major genetic component in its transmission. In addition to its genetic determination, schizophrenia is also associated with increased morbidity and mortality with illness and suffering and with death rates that are higher than would be expected. One of the intriguing possibilities is that there may be some biological link between genetic predisposition to schizophrenia and to other medical diseases. This research on medical comorbidity, originally presented at the Tenth Annual Pennsylvania Conference on Schizophrenia at Norristown State Hospital, requires further research and understanding.

The psychiatric disorders of midlife.

The midlife phase of adult development, once viewed as a period of stagnation and involution, is now seen as a time with the potential for significant psychologic growth and development. The concept that women's psychologic health and physical health are closely tied to her reproductive function is coming under close scrutiny. The menopause is only one variable, along with other biologic, psychologic, and sociocultural stressors, that increases the individual woman's vulnerability to several psychiatric disorders. Careful attention to the patient's presenting symptoms and the specific diagnostic criteria for psychiatric illnesses allows for accurate diagnosis and treatment and avoids the pitfall of attributing these symptoms to the "menopausal syndrome."

Stress, affective disorders, and immune function.

Increasing scientific evidence supports age-old observations that psychosocial factors are closely associated with the pathogenesis of certain physical and mental illnesses. The immune system appears to play a primary mediating role. Whereas acute stress may initiate a transient immunologically protective response, prolonged or poorly controlled psychosocial stressors may result in depression of different components of the immune system. These responses may be related to, or independent of, changes in the neuroendocrine system. As the rather prolific literature in this infant area of psychoneuroimmunology reveals, there are many complex levels of interaction that require further investigation. There is clearly a need for long-term prospective studies that will identify individuals at risk for those numerous diseases in which psychosocial factors and impaired immune function play a pathogenic role. In addition to correlating altered immune function over time with changes in the physical environment, these studies should include psychologic profiles, life-event inventories, and psychiatric interviews in an effort to delineate the role of psychosocial factors as the stimulus for and as the response to the disease process. One of the many positive outcomes of this multifactorial approach to illness is that it will alter the physician's approach to disease and thus to patients as they are evaluated and treated in the psychosocial context in which they live. As Hippocrates said, "It is more important to know what sort of a person has a disease than to know what sort of disease a person has."

Psychologic factors associated with peptic ulcer disease.

Peptic ulcer disease provides an excellent model for the study of mind-body interactions in the pathogenesis and course of an illness. Early psychodynamic explanations of the role of personality factors in the evolution of peptic ulcer disease have been supplemented in recent years by more scientifically based studies on the role of stress and coping ability. Multiple psychosocial variables have confounded the outcome of many of these studies. Yet, a clear need and guidelines exist for the comprehensive medical and psychosocial evaluation and treatment of patients with peptic ulcer disease. Concomitant psychiatric assessment and management, including psychotherapeutic and psychopharmacologic approaches, for those patients with refractory symptoms or ongoing psychiatric symptoms carried out in close collaboration with primary caregivers will significantly decrease overall morbidity and mortality.

Evolving concepts of psychopathology in inflammatory bowel disease. Implications for treatment.

The role of psychiatric factors in inflammatory bowel disease has been increasingly relegated, according to Aronowitz and Spiro, to "patient's illness, but not to disease, to therapy, but not to etiology, to symptoms, but not to pathology, and finally to the course of the disease, but not to its cause." This is not surprising in view of the fact that to attribute psychological factors to an illness is seen by the patient and physician alike as an attempt to "blame the victim." As a result, there has been a concerted effort in the past two decades in the field to replace the seemingly archaic, developmental, romantic psychoanalytic concepts of causation with more "enlightened," "scientific" paradigms of psychoneuroimmunology and psychiatric comorbidity. Despite major advances in the biomedical understanding of inflammatory bowel disease and its treatment, however, the essential questions about the complex relationship between emotional and physical symptoms remain a source of frustration both to the patient and to the treating physician in the management of the chronic diseases of the bowel. Thus, early assumptions of a psychogenic basis of ulcerative colitis and Crohn's disease may have been imprecise, but the genuine contributions of investigators such as Alexander, Karush, and Engels ought not to be cast aside completely. Experience with the treatment of patients with inflammatory bowel disease shows that attention to psychiatric comorbidity, quality of adaptation to illness, and the patient-physician relationship are essential components of a comprehensive, successful approach to these chronic illnesses.

Redesigning the surgery clerkship at MCP Hahnemann School of Medicine to address the educational needs of generalists.

This article describes how the surgery clerkship at MCP Hahnemann School of Medicine was redesigned to provide all students a well-rounded general professional education and to address the specific educational needs of generalists. During the 12-week clerkship, students spend eight weeks on two different general surgery rotations, which include significant experiences in outpatient settings. The evaluation and management of common general surgical problems, as well as the holistic approach to patient care, are emphasized. A nurse educator, recruited through funding obtained from The Robert Wood Johnson Foundation's Generalist Physician Initiative, provides formal instruction in holistic care and teaches bedside procedures. Two weeks are devoted to focused surgical subspecialty experiences addressing common conditions and are conducted primarily in outpatient settings. The remaining two weeks include an integrated musculoskeletal disease rotation, including orthopaedic surgery, rheumatology, physiatry, and radiology. Didactic teaching includes criteria for referral of patients from generalists to specialists. The new clerkship model has been well received by the students. Review of student logs for the first six months indicates the breadth of surgical experience has been maintained and appropriate balance achieved between simple and complex surgical cases. Further evaluation of the model will continue through longitudinal follow-up.

Hypnosis on a consultation-liaison service.

The use of hypnosis was demonstrated on a psychiatric consultation-liaison service (CLS) in a broad spectrum of medically hospitalized patients. Hypnosis was employed as an adjuvant measure to traditional medical and psychologic treatment modalities. Tapes for autohypnosis were used for reinforcement. Twenty-nine women and eight men from 24 to 75 years of age were hypnotized for relief of depression, pain, anxiety, or side-effects from chemotherapy. Results were excellent (total to almost total relief of symptoms) in 68% of the patients, fair in 22%, and poor in 11% with no differences among the results with the various conditions. This report demonstrates that hypnotherapy can be an extremely useful tool in the medical management of patients on a CLS.

Noncompliance in the treatment of endocarditis. The medical staff as co-conspirators.

Intravenous drug abusers with endocarditis present difficult problems in both medical and psychiatric management. A retrospective chart survey revealed that eight of nine such patients with endocarditis signed out against medical advice before antibiotic therapy was completed. Reasons for premature discharge included the patient's underlying psychopathology as well as the emotional response of the staff to these patients. Understanding both of these factors may help to prevent these premature discharges.

Beneficial effects of psychiatric intervention on recovery after coronary artery bypass graft surgery.

The effects of perioperative psychiatric intervention were studied in 33 patients undergoing coronary artery bypass graft (CABG) surgery. All patients were evaluated preoperatively using the Mini-Mental State Exam and the Psychological Adjustment to Illness Scale-Self-Report. Participants in the study group (N = 16) had a structured psychiatric interview prior to surgery and were followed daily with supportive psychotherapy throughout their hospitalization. The number of medical complications was higher in the control group. No significant differences were found in neurologic or psychologic complications. The study group used significantly more oxycodone-acetaminophen (Percocet), but less morphine-sulfate or benzodiazepine on postoperative days 3, 4, and 6. The mean length of stay was 3 days shorter for patients in the study group. In the current era of escalating health care costs and high technology, clinical protocols and research studies that evaluate the cost effectiveness and efficacy of psychiatric intervention in medically ill patients should be pursued.

[Housing quality in cities from the tenant's point of view]. / Städtische Wohnqualität aus der Sicht der Bewohner.

Since the demand for higher quality of live has been the big discussion, also the call for a more livable city has become more and more frequent. For urban development policy it is necessary to workout conceptionally the different demands for a higher living quality. First it is essential to define the content of the term Quality of Live. In this article one tries to show how the term is broken-up in it's components and how it can be empirically tested with help of indicators. Results from different studies show what the needs of the inhabitants are and how much weight the different quality components have for different population groups. The results show that in all groups of inhabitants-aside from the superior features of a city (infrastructure)-the component living environment plays an important role. If it is rated in a negative sense, it is often the ground of leaving the city-especially for families.

Hypnosis as an aid for tinnitus patients.

This study was undertaken to evaluate hypnosis versus stress management as therapeutic modalities in the treatment of tinnitus. Participants were recruited from the local tinnitus association and the Otolaryngology Division of the Department of Surgery. The instruments were the following standardized tests (NIMH Diagnostic Int. Schedule; SCL 90R, Beck Depression Inventory) in addition to a tinnitus questionnaire. Improvement was shown on 5 separate scales, some alleviated by both types of treatment and others singularly by hypnosis or stress management. The data reinforce the use of behavioral techniques and suggest that different techniques may be more appropriate for specific symptoms.

Distinguishing features of pseudocomplex partial seizures.

The authors identify common features in the clinical presentations of three patients whose pseudoseizures mimicked complex partial seizures. All three had suffered the recent traumatic loss of a significant love object, and all manifested unconscious feelings of guilt and the use of defense mechanisms of denial, dissociation, introjection, identification, and symbolization. The authors explore the diagnostic, treatment, and etiological implications of these findings.