bluuebunny/crossref_metadata_2025 huggingface dataset:
Humor in hospice care: Who, where, and how much?
Authors: Adamle Kathleen N. , Ludwick Ruth
Published: May 2006

Humor has been identified as an intrinsic social phenomenon occurring in all groups throughout human history. It is among the most prevalent forms of human social behavior yet one of the least understood or defined. Although researchers in a number of disciplines have studied the effects of humor on patients, limited work has focused on end-of-life care. The present study investigated social interactions involving humor in hospice settings using nonparticipant observation. Results revealed that humor was present in 85 percent of 132 observed nurse-based hospice visits. Of these, hospice patients initiated humor 70 percent of the time. These findings were consistent regardless of hospice setting. Humor was spontaneous and frequent, and instances of humorous interactions were a prevalent part of everyday hospice work.
Spiritual well-being as a dimension of quality of life for patients with advanced cancer and AIDS and their family caregivers: Results of a longitudinal study
Authors: Sherman Deborah Witt , Ye Xiang Y. , McSherry Christina , Calabrese Miriam , Parkas Valerie , Gatto Maria
Published: May 2006

Based on a longitudinal, quality-of-life study, this article presents pilot data regarding the spiritual well-being of patients with advanced cancer or AIDS and their family caregivers. Data include similarities and differences between the patient and caregiver populations and patient/family caregiver dyads as well as trends with regard to changes in spiritual well-being during the illness and dying process. The reliability of the Spiritual Well-Being Scale 1 was examined for patient and caregiver groups, as was the relationship between selected demographic variables and spiritual well-being. Implications for practice are discussed.
Providing hospice care in rural areas: Challenges and strategies
Authors: Casey Michelle M. , Moscovice Ira S. , Virnig Beth A. , Durham Sara B.
Published: May 2006

Hospices in rural settings face challenges in the provision of hospice care as a result of their location and the size of their service area population. To ascertain the challenges that hospices face in serving rural communities, researchers conducted in-depth case studies of four different models of hospice care in rural areas. The authors describe strategies used by the case study hospices and recommend policies that could increase access to hospice care for rural Medicare beneficiaries and other rural residents. National initiatives to improve end-of-life care need to consider the special challenges faced by rural hospices.
For It Is In Giving That We Receive
Authors: Anderson Mary L. , Smit Eileen M.
Published: May 2006

Our colleague, Sharon, wanted to die at her camp far away from hospitals and machines. Helping her to die demonstrated how caring is a reciprocal process. As we gave Sharon help and support, wereceived much in return. Sharon helped us to grow as we coped with her dying. This anecdotal story describes specific caring behaviors and communication skills used by the team members to help Sharon and each other grow during the terminal stages of her illness.
Medicare hospice cost reports yield inaccurate data
Authors: Tenney Richard C. , Cotton Kenneth E.
Published: May 2006

A widely quoted statement among providers “we lose money on the Medicare hospice benefit (HB)” is often cited as the reason why more hospices are not participants in the Medicare program. We began this study to detennine the validity of this statement. Our study examined 1987 Medicare cost reports of 15 Colorado hospices to determinerecent costs and compare costs to payment rates. We found that data collected by the cost report isfundamentally inadequate to accurately apportion all Medicare costs. There is an adequatemethodfor only direct salaiy costs. No adequate methods are availablefor other direct costs, such as durable medical equipment-(DME),supplies, ordrugs. There is no way to accurately allocate administrative and general expenses amongthe modalitiesofcare. Methods of segregating Medicare-disallowed costs, such asfundraising, are not adequate to allow these to be properly identified. A cooperative effort is proposed that would unite the hospice community in developing cost accountingreports that can be used inaccurate cost finding and rate setting. Suggested team members are the Health Care Financing Administration (HCFA), the Colorado Hospice Organization (CHO), National Hospice Organization (NHO) and other organizations, hospiceproviders, and consultants.
Non-invasive pain control in the terminally ill patient
Authors: Kinzbrunner Barry M. , Policzer Joel , Miller Barbara , Neiber Linda
Published: May 2006

Although terminal patients with chronic pain are best managed with oral analgesia, patients who cannot take oral medication of ten receive treatment liy parenteral routes.

Seventy consecutive terminal patients admitted to our hospice inpatient facility were evaluatedfor pain control over a three day period. Level ofpain was evaluated on a scale of zero to three (0=no pain, 1=mild pain, 2=moderate pain, 3=severe pain). Patients were also evaluated for level of consciousness on a scale of one to four (1=alert, 2=confused, 3=semi-comatose, 4=comatose). Patients were medicated with morphine sulfate, either orally or by suppository, on a regular, four-hour schedule. Level of pain and level ofconsciousness evaluations were performed at the time each dose of morphine sulfate was administered.

Data were compared for the level of pain and level of consciousness for the three day study period using Chisquared analysis. The results showed a significant decrease in levelofpain over the study period (p<.005). During this time, no significant alteration in level of consciousness was noted. Thirtynine out of 65 patients were treated via the suppository route and a significant decrease in the level of pain was seen in this sub-group as well (p<.005). Median morphine sulfate dose in all patients on day three was 15 mg. every four hours, with no significant difference between oral and suppository sub-groups. Parenteral analgesia was not required by any patient to achieve adequate pain control.

This study demonstrates that effective pain control in terminal patients can be achieved withoutparenteral administration of analgesia and without alteration in level of consciousness. In patients unable to receive oral analgesia, the use of suppository analgesia is an effective alternative, avoiding the increased discomfort associated with parenteral analgesia administration.
Beyond hospice care: A survey of community outreach programs
Authors: Petersen Suni
Published: May 2006

In an editorial by David Lescohier (The American Journal of Hospice & Palliative Care), the tough dilemma faced by many hospices today is our acceptance into the mainstream of the medical delivery system. Hospitals have found that offering specialized adjunct programs has helped them maintain an edge in a competitive environment. Part I of this article contains the results of a national survey which explored the differences in the hospices that are pursuing outreach programs and the direction of those programs. Part II provides results and discussion of the benefits, obstacles and problems in several types of outreach: counseling, schools, prehospice and day care.
Use of a thromboxane synthetase inhibitor in the presence of dermal pressure
Authors: Swaim Steven F. , Vaughn Dana M. , Riddell Kay P. , Powers Robert D.
Published: May 2006

Preliminary research was conducted to ascertain the potential for a thromboxane synthetase inhibitor (TSI) in preventing the early histopathologic and biochemical changes associated with impending dermal pressure injury. In the presence of dermal pressure over a bony prominence in greyhound dogs, a systemically administered TSI resulted in lower dermal levels of thromboxane A2 (TxA2) and an absence of histopathologic lesions when compared to dogs receiving a placebo. The results indicate a potentialfor TSIs as adjunctive therapy in the prevention of decubital ulcers by counteracting the TxA2-related vasoconstriction and thrombosis with their resultant ischemic necrosis of the skin.
Hospice care versus home health care: Regulatory distinctions and program intent
Authors: Tierney Jeanne , Wilson Damien
Published: May 2006

A significant percentage of community health care agencies have both a certified hospice and home health program component. These agencies commonly utilize many of the same “cross-trained” staff in both programs. However these programs are not identical in focus, scope and regulatory practice. This paper examines both certified hospice and certified home health care practice from the standpoint of the Code of Federal Regulations (CFR). The distinctions made in these two sets of regulations (hospice, 42 CFR 418.50 -.100 and home health, 42 CFR 484.10 -.52) point to important differences in program and management practice.
Symbols of transformation at the boundary of life
Authors: Grey Richard
Published: May 2006

In the process of engaging in spiritual care of the terminally ill it occasionally happens that deeply religious patients use picturesque, sometimes discordant language to describe some matter of concern to them. These images on close scrutiny appear to be archetypal in nature, vehicles for the expression of some deeper, personal truth at work within them. Such matters may escape the listener who is not willing to consider the unusual, nor to search out the possible symbolic nature of such utterances. A common thrust of such language among the deeply religious appears to be the suggestion of a final transformation in their inner life from conflicted and qualified hope in a spiritual reality to unconflicted and unqualified trust in this.
Relationship between right-to-die and satisfaction with life
Authors: Huber Ruth
Published: May 2006

To examine the relationship between right-to-die attitudes and satisfaction with life, 108 institutionalized elderly residents in a random sample were interviewed inthe summer of 1990.’ Overall, 55 percent responded Yes or Probably Yes to a question pertaining to the legalization of some form of control of death circumstances. Those who were moderately or most satisfied with their lives more often responded Yes or Probably Yes to the legalization question.

The purpose of this article is to discuss findings from a random sample of 108 institutionalized elderly concerning the relationship between their responses to right-to-die questions and their self-reported satisfaction with life.
Pain, music creativity and music therapy in palliative care
Authors: O’Callaghan Clare C.
Published: May 2006

An analysis of the music therapy literature yields numerous reports to support the role of music in the alleviation of pain in palliative care. Four theoretical perspectives that support why many patients report reduced pain sensation after music therapy include: the psychological relationship between music and pain; the psychophysiological theory; spinal mechanisms involved in pain modulation; and the role of endorphins. Considerations significant to the use of music in pain relief include how music, used in appropriately, can aggravate pain sensation. Case studies, which include the use of creative music therapy techniques, point to the efficacy of music therapy in alleviating the pain experiences of both palliative care patients and their significant others.
Hospice care or assisted suicide: A false dichotomy
Authors: Miller John L.
Published: May 2006

In this paper, the author argues that making assisted suicide available is not a contradictory position to espousing hospice care. He draws on historical and political examples to explain the ethical basis for this assertion. By defining the issue at stake as one of personal autonomy (the loss or gain thereof), the author challenges the argument that making assisted suicide available leads to a slippery slope towards euthanasia, eugenics, or genocide. He asserts that narrowing choices by preventing people from seeking assistance in suicide is more likely to lead us down the slippery slope towards coercive medical and state intervention in our lives.
Comfort care: A framework for hospice nursing
Authors: Vendlinski Susanne , Kolcaba Katharine Y.
Published: May 2006

Provision of comfort is paramount to the practice of hospice nurses. However, the approach to meeting needs holistically is often intuitive or based on multidisciplinary rather than nursing models. A review of the nursing literature identified only one article describing the application of a nursing framework to hospice nursing practice. The purpose of this article is to describe a theory of comfort care that offers definitions and a grid for the art of comfort care that are relevant to hospice nursing practice. Using Kolcaba’s framework of holistic comfort, nurses can be comprehensive and consistent in assessing comfort and in designing interventions to enhance the comfort of patients and families. The content domain of holistic comfort is conceptualized as interrelated parts (types and contexts) as they are experienced simultaneously. The framework of comfort care, which includes the content domain and the theory of comfort, is explained and applied through the presentation of a hospice case study. Potential application of the framework to hospice research is proposed.
Occupational stress in hospice care: Causes and coping strategies
Authors: Dean Ruth A.
Published: May 2006

Thirty-three nurses from three hospice services in a large Midwestern city participated in this study, which investigated responses to difficult or demanding work-related situations. Three tools (the Self Inventory of Situational Responses-TC questionnaire, the Spielberger State Anxiety Inventory questionnaire and a rank-ordered listing of likely causes of difficult or demanding situations) were used to collect data. Findings indicated that anxiety is an issue for hospice workers but that difficult or demanding situations were viewed as challenges rather than threats. Management of intractable symptoms and communication issues were of primary concern. Administrative concerns were identified as the third-ranking source of difficult situations. Issues related to death and dying were of notably less concern. Strategies for staff support also are identified.
Believing in patients’ beliefs: Physician attunement to the spiritual dimension as a positive factor in patient healing and health
Authors: Hamilton David G.
Published: May 2006

The spiritual dimension has been demonstrated by research to be an important and fundamental aspect of human functioning, one that positively affects healing and health and should be mobilized as an active part of the health care of persons. Moreover, physicians have an obligation to acknowledge the potential role of spirituality in the health and healing of patients and to form a therapeutic alliance with patients that takes their spirituality into account and affirms its importance. Questions about persons’ spiritual beliefs and practices, their values, and what they consider meaningful in their lives should become part of the initial medical interview and an ongoing focus in the physician-patient relationship.
Intermittent subcutaneous injections of pain medication: Effectiveness, manageability, and satisfaction
Authors: Letizia Marijo , Shenk JoAnn , Jones Tammy Dee
Published: May 2006

This study describes the use of intermittent subcutaneous injections of medications for pain control in a home hospice program. Six questionnaires were used to collect data over a one-year time period on the 52 patients who received medications by this route. Eighty-four percent of those patients had a diagnosis of cancer; patients received hospice care for a mean of 25 days. On average, intermittent subcutaneous medications were instituted three days prior to the patient’s death. The main indication for this route was difficulty swallowing. Morphine was the most frequently used drug; side effects from the medication and problems with the route were rarely reported. Demographic information was collected on both the nursing staff and patients’ caregivers; analysis indicated that caregivers were able to manage the injections and were satisfied with the method. Assessment of pain prior to and following the injections demonstrated the effectiveness of this method in controlling patients’ pain.
Student-led exercise sessions yield significant fitness gains for Alzheimer's patients
Authors: Arkin Sharon M.
Published: May 2006

At a time when they are losing skills in virtually all arenas of life, persons with Alzheimer's disease can experience significant, esteem-building achievements in physical fitness and mood through supervised participation in an exercise program. The effects of physical exercise plus cognitive and social stimulation on persons with early stage Alzheimer's disease were assessed in a longitudinal study. Twenty-four such individuals, aged 54 to 88 at program entry, participated in 16 to 20 exercise sessions and 10 community activity sessions per semester for two to eight semesters. Half of the weekly exercise sessions included memory and language stimulation activities. Students, supplemented by family caregivers, supervised the sessions. Exercise sessions consisted of flexibility, balance, aerobic, and weight resistance activities. Preparticipation and semiannual post-testing of aerobic fitness and duration and upper and lower body strength was done.

Highly significant fitness gains (p < .001) were achieved in the six-minute walk test, upper and lower body strength, and duration of aerobic exercise. Five participants, aged 86 to 91, completed six to eight semesters and were doing 27 to 45 minutes of aerobics per session at program's end. Five participants scored within the normal range for age-matched healthy active adults on the sixminute walk test at baseline. Nine others achieved and three exceeded the normal range during treatment. Cognitive decline was slowed and mood improved. Firstyear cognitive outcomes have been published elsewhere. 1-4 An article reporting final cognitive outcomes is in preparation; Outcome data is summarized on the project website: www.u.arizona.edu/~sarkin/elderrehab.html.

The benefits of physical exercise can be made available at nominal cost to Alzheimer's patients and other elderly persons by using students to provide transportation, supervision, and the motivational support that is key to exercise adherence. Further research is needed to determine the relative contributions of each program component to the positive outcomes.
Effect of design interventions on a dementia care setting
Authors: Schwarz Benyamin , Chaudhury Habib , Tofle Ruth Brent
Published: May 2006

This study examined the effects of particular design interventions in a long-term care facility on residents with dementia and staff perceptions of care delivery. Major renovations were carried out in a care facility in the Midwestern United States. Renovations included a new addition of a dementia care unit designed as a cluster of resident rooms around living and dining areas, and two renovated wings with decentralized dining areas. The research methods used in the study included environmental assessment with the Professional Environmental Assessment Protocol (PEAP), behavioral mapping, and focus-group interviews with staff members. The renovated environment scored higher in PEAP and was perceived by the staff members as a more homelike setting. Although behavioral observations indicate that there was more involvement in programmed activities by the residents, the decentralized neighborhood design did not meet all the behavioral expectations due to a lack of appropriate activities, high staff turnover, and family members' resistance to the relocation of their loved ones. Organizational commitment, advanced planning for appropriate staffing levels, and dementia-related training is crucial for fuller realization of the potential of a household design.
Relationship matters in demantia caregiving
Authors: Lewis Marsha L. , Hepburn Kenneth , Narayan Suzanne , Kirk Laura Nelson
Published: May 2006

This study examined the relationship between four framing categories of caregiving (Relational, Instrumental, Reactive, Role Acquiring), derived from interviews with spouse caregivers, and scores on standardized measures of responses to and outcomes of caregiving. Participants were 132 spouses recruited into a larger intervention study of family caregivers of communitydwelling persons with dementia. Qualitative data were analyzed using constant comparative method; quantitative data were analyzed using one-way analysis of variance (ANOVA). Findings demonstrated that relational spouses scored better than spouses in the other three categories, indicating greater positive well-being. Relational spouses also scored significantly lower than instrumental and reactive spouses on a composite caregiver distress measure (p = 0.003). These results suggest that interventions may need to be tailored to spouses with different caregiving perspectives.
Interstitial uniparental isodisomy at clustered breakpoint intervals is a frequent mechanism of NF1 inactivation in myeloid malignancies
Authors: Stephens Karen , Weaver Molly , Leppig Kathleen A. , Maruyama Kyoko , Emanuel Peter D. , Le Beau Michelle M. , Shannon Kevin M.
Published: May 2006

To identify the mechanism of loss of heterozygosity (LOH) and potential modifier gene(s), we investigated the molecular basis of somatic NF1 inactivation in myeloid malignancies from 10 children with neurofibromatosis type 1. Loci across a minimal 50-Mb region of primarily the long arm of chromosome 17 showed LOH in 8 cases, whereas a less than 9-Mb region of loci flanking NF1 had LOH in the remaining 2 cases. Two complementary techniques, quantitative polymerase chain reaction (PCR) and fluorescence in situ hybridization (FISH), were used to determine whether the copy number at loci that showed LOH was 1 or 2 (ie, deleted or isodisomic). The 2 cases with LOH limited to less than 9 Mb were intrachromosomal deletions. Among the 8 leukemias with 50-Mb LOH segments, 4 had partial uniparental isodisomy and 4 had interstitial uniparental isodisomy. These isodisomic cases showed clustering of the centromeric and telomeric LOH breakpoints. This suggests that the cases with interstitial uniparental isodisomy arose in a leukemia-initiating cell by double-homologous recombination events at intervals of preferred mitotic recombination. Homozygous inactivation of NF1 favored outgrowth of the leukemia-initiating cell. Our studies demonstrate that LOH analyses of loci distributed along the chromosomal length along with copy-number analysis can reveal novel mechanisms of LOH that may potentially identify regions harboring “cryptic” tumor suppressor or modifier genes whose inactivation contributes to tumorigenesis.
The Follicular Lymphoma International Prognostic Index (FLIPI) separates high-risk from intermediate- or low-risk patients with advanced-stage follicular lymphoma treated front-line with rituximab and the combination of cyclophosphamide, doxorubicin, vincristine, and prednisone (R-CHOP) with respect to treatment outcome
Authors: Buske Christian , Hoster Eva , Dreyling Martin , Hasford Joerg , Unterhalt Michael , Hiddemann Wolfgang ,   for the German Low Grade Lymphoma Study Group (GLSG)
Published: May 2006

The Follicular Lymphoma International Prognostic Index (FLIPI) was developed to predict prognosis of patients with follicular lymphoma (FL). However, it was based on different protocols, none of which included rituximab. The current analysis aimed at evaluating the predictive value of the FLIPI for treatment outcome in 362 patients with advanced-stage FL treated front-line with rituximab/CHOP in a prospective trial of the German Low Grade Lymphoma Study Group. According to the FLIPI, 14% of the patients were classified as low-risk, 41% as intermediate-risk, and 45% as high-risk patients. With a 2-year time to treatment failure (TTF) of 67%, high-risk patients had a significantly shorter TTF as compared with low- or intermediate-risk patients (2-year TTF of 92% and 90%, respectively; P < .001). Our data demonstrate that the FLIPI is able to identify high-risk patients with advanced-stage FL after first-line treatment with rituximab/chemotherapy.
Targeted gene deletion demonstrates that the cell adhesion molecule ICAM-4 is critical for erythroblastic island formation
Authors: Lee Gloria , Lo Annie , Short Sarah A. , Mankelow Tosti J. , Spring Frances , Parsons Stephen F. , Yazdanbakhsh Karina , Mohandas Narla , Anstee David J. , Chasis Joel Anne
Published: May 2006

Erythroid progenitors differentiate in erythroblastic islands, bone marrow niches composed of erythroblasts surrounding a central macrophage. Evidence suggests that within islands adhesive interactions regulate erythropoiesis and apoptosis. We are exploring whether erythroid intercellular adhesion molecule 4 (ICAM-4), an immunoglobulin superfamily member, participates in island formation. Earlier, we identified αV integrins as ICAM-4 counterreceptors. Because macrophages express αV, ICAM-4 potentially mediates island attachments. To test this, we generated ICAM-4 knock-out mice and developed quantitative, live cell techniques for harvesting intact islands and for re-forming islands in vitro. We observed a 47% decrease in islands reconstituted from ICAM-4 null marrow compared to wild-type marrow. We also found a striking decrease in islands formed in vivo in knock-out mice. Further, peptides that block ICAM-4/αV adhesion produced a 53% to 57% decrease in reconstituted islands, strongly suggesting that ICAM-4 binding to macrophage αV functions in island integrity. Importantly, we documented that αV integrin is expressed in macrophages isolated from erythroblastic islands. Collectively, these data provide convincing evidence that ICAM-4 is critical in erythroblastic island formation via ICAM-4/αV adhesion and also demonstrate that the novel experimental strategies we developed will be valuable in exploring molecular mechanisms of erythroblastic island formation and their functional role in regulating erythropoiesis.
Failure of non-invasive ventilation in patients with acute lung injury: observational cohort study
Authors: Rana Sameer , Jenad Hussam , Gay Peter C , Buck Curtis F , Hubmayr Rolf D , Gajic Ognjen
Published: May 2006

Introduction

The role of non-invasive positive pressure ventilation (NIPPV) in the treatment of acute lung injury (ALI) is controversial. We sought to assess the outcome of ALI that was initially treated with NIPPV and to identify specific risk factors for NIPPV failure.

Methods

In this observational cohort study at the two intensive care units of a tertiary center, we identified consecutive patients with ALI who were initially treated with NIPPV. Data on demographics, APACHE III scores, degree of hypoxemia, ALI risk factors and NIPPV respiratory parameters were recorded. Univariate and multivariate regression analyses were performed to identify risk factors for NIPPV failure.

Results

Of 79 consecutive patients who met the inclusion criteria, 23 were excluded because of a do not resuscitate order and two did not give research authorization. Of the remaining 54 patients, 38 (70.3%) failed NIPPV, among them all 19 patients with shock. In a stepwise logistic regression restricted to patients without shock, metabolic acidosis (odds ratio 1.27, 95% confidence interval (CI) 1.03 to 0.07 per unit of base deficit) and severe hypoxemia (odds ratio 1.03, 95%CI 1.01 to 1.05 per unit decrease in ratio of arterial partial pressure of O2 and inspired O2 concentration – PaO2/FiO2) predicted NIPPV failure. In patients who failed NIPPV, the observed mortality was higher than APACHE predicted mortality (68% versus 39%, p < 0.01).

Conclusion

NIPPV should be tried very cautiously or not at all in patients with ALI who have shock, metabolic acidosis or profound hypoxemia.
Estrogen Regulation of the Glucuronidation Enzyme UGT2B15 in Estrogen Receptor-Positive Breast Cancer Cells
Authors: Harrington William R. , Sengupta Surojeet , Katzenellenbogen Benita S.
Published: May 2006

Estrogens and androgens influence many properties of breast cancer cells; hence, regulation of local estrogen and androgen levels by enzymes involved in steroid hormone biosynthesis and metabolism would impact signaling by these hormones in breast cancer cells. In this study, we show that the UDP-glucuronosyltransferase (UGT) enzyme UGT2B15, a member of the UGT family of phase II enzymes involved in the glucuronidation of steroids and xenobiotics, is a novel, estrogen-regulated gene in estrogen receptor (ER)-positive human breast cancer cells (MCF-7, BT474, T47D, and ZR-75). UGT2B15 is the only UGT2B enzyme up-regulated by estrogen, and marked estradiol stimulation of UGT2B15 mRNA levels is observed, in a time- and dose-dependent manner. UGT2B15 stimulation by estradiol is blocked by the antiestrogen ICI182,780, but not by the translational inhibitor cycloheximide, indicating that UGT2B15 is likely a primary transcriptional response mediated through the ER. UGT2B15 up-regulation is also evoked by other estrogens (propylpyrazoletriol, genistein) and by the androgen 5α-dihydrotestosterone working through the ER, but not by other steroid hormone receptor ligands. Western blot and immunocytochemical analyses with several UGT2B-specific antibodies we have designed and steroid glucuronidation assays indicate a large increase in both cellular UGT2B15 protein and enzyme activity after estrogen treatment. Due to the important role of UGT enzymes in forming conjugates between steroids and glucuronic acid, thereby inactivating them and targeting them for removal, the estrogen-induced up-regulation of UGT2B15 might have a significant moderating effect on estrogen and androgen concentrations, thereby reducing their signaling in breast cancer cells.
A New Photoisomerization Process of the 4-Cyanobutyl Group in a Cobaloxime Complex Crystal Observed by Neutron Diffraction
Authors: Hosoya Takaaki , Uekusa Hidehiro , Ohashi Yuji , Ohhara Takashi , Kuroki Ryota
Published: May 2006

The 4-cyanobutyl group of (4-cyanobutyl)[3,4-lutidine](dimethylglyoximato)[O-(diphenylboryl)dimethylglyoximato]cobalt(III) was isomerized to the 1-cyanobutyl group with retention of the single-crystal form, although the corresponding cobaloxime complex without diphenylboryl in the equatorial ligands did not show such a photoisomerization. The trans–cis–cis conformation of the 4-cyanobutyl group caused by the steric repulsion from the diphenylboryl group is favorable to the crystalline-state reaction. In order to elucidate the detailed isomerization mechanism, two hydrogen atoms of the 4-cyanobutyl group were replaced with the deuterium atoms such as –CH2CH2CH2CD2CN. After the photoisomerization, the crystal structure with deuterated 4-cyanobutyl group was analyzed by neutron diffraction. Only one of the two deuterium atoms of the 4-cyanobutyl group was transferred to the C1 atom such as –CD(CN)CH2CH2CDH2. This result made clear that the photo-produced cyanobutyl radical turned upside down after homolytic cleavage of the Co–C bond, and then the Co(II) atom and the radical made a bond to form the 1-cyanobutyl group.
Component Analysis of Particulate Products in Electron Beam-Irradiated Xylene/Air Mixtures Using an Atmospheric Pressure Ionization Mass Spectrometer
Authors: Hakoda Teruyuki , Sako Toshihiro , Shimada Akihiko , Ishida Tsuneo , Kojima Takuji
Published: May 2006

Particulate and gaseous organics are formed, as transient products, from dilute concentrations of xylene in air under electron beam irradiation; however, the components of the particulate organic products and the particle formation process are unknown. In the present study, the component analysis of particulate products were performed employing an atmospheric pressure ionization mass spectrometer (APIMS) based on a temperature-programmed desorption method to identify the components of the particles from o-xylene as a function of their gasification temperatures. Ions of 139–203 u with a peak interval of the m/z of 16 u, the same as the value of O+, were observed as vaporized particle components at correspondent temperatures. The ions of 43, 47, 61, 97, 111, 135, and 139 u were detected as the vaporized components at 333 K. The ions of 155, 171, and 187 u were observed at 363 K, besides that of 203 u at 393 K. The ions of 392–421 u were also appreciable with peak heights of 10−2 order lower than those for the ions of 139–203 u at temperatures higher than 393 K. The gaseous products in irradiated o-xylene/air mixtures were also analyzed with the APIMS. The ions with m/z lower than 139 u were detected as gaseous products.
On the Stereoselectivity of Asymmetric Strecker Synthesis in a Cyclohexane System: Synthesis of Optically Active cis- and trans-1-Amino-2-hydroxycyclohexane-1-carboxylic Acids
Authors: Shinada Tetsuro , Kawakami Tadashi , Sakai Hiroshi , Matsuda Hiromi , Umezawa Taiki , Kawasaki Masaki , Namba Kosuke , Ohfune Yasufumi
Published: May 2006

Stereoselective synthesis of both optically active cis- and trans-1-amino-2-hydroxycyclohexane-1-carboxylic acids (Ahhs) 1a and 1b was accomplished by an asymmetric version of the Strecker synthesis. Stereochemical aspects of their chiral induction processes are investigated.
Isolation and Physical Properties of an Electron-Rich 3,4-Diacetoxy-8,8-dimethylheptafulvene
Authors: Yin Bing Zhu , Mori Akira , Takeshita Hitoshi , Inoue Hironao
Published: May 2006

An electron-rich 3,4-diacetoxy-8,8-dimethylheptafulvene was isolated. The crystal structure shows that the seven-membered ring exists in an “envelope” conformation and the exocyclic C=C bond length is 1.343 Å.
Conjugate Addition of Allylic Groups to α,β-Enones via Photoinduced Electron Transfer Reaction of Allylic Stannanes
Authors: Takuwa Akio , Nishigaichi Yutaka , Iwamoto Hidetoshi
Published: May 2006

Conjugate addition of allylic groups, including allyl and cinnamyl systems, to a variety of α,β-unsaturated ketones could be achieved by photoirradiation with allylic stannanes.
Thermotropic Liquid-Crystalline Copolymers Containing Ionic Group
Authors: Ujiie Seiji , Tanaka Yutaka , Iimura Kazuyoshi
Published: May 2006

Thermotropic liquid-crystalline copolymers containing an ionic group have been synthesized, and the effects of the ionic component for their liquid-crystalline properties have been studied.
Living Ring-opening Oligomerization of Cyclosiloxanes with an Aluminum-Tetraphenylporphyrin Complex Initiator
Authors: Yoshinaga Kohji , Iida Yoshikazu
Published: May 2006

An aluminum-tetraphenylporphyrin (Al(TPP)) catalyzed the ring-opening oligomerization of cyclosiloxanes with narrow molecular weight distribution, involving selection as for ring-size.
Catalytic Behavior of Iron(III)-8-quinolinol Complex in the Chemiluminescence Reaction of Luminol with Hydrogen Peroxide in Reverse Micelles
Authors: Fujiwara Terufumi , Tanimoto Noriyuki , Nakahara Kazue , Kumamaru Takahiro
Published: May 2006

Upon mixing of tris(8-quinolinolato)iron(III), an enhancement in the chemiluminescence emission resulting from the luminol-hydrogen peroxide reaction in reversed micellar solution was observed. Uptake of the complex by reverse micelles and its subsequent decomposition in the micelles appear to occur easily in the process.
Novel [4+2]-Type Reaction of 2-(Dimethylamino)cyclobutanecarboxylic Esters with Carbonyl Compounds
Authors: Shimada Shigeru , Saigo Kazuhiko , Nakamura Hideyuki , Hasegawa Masaki
Published: May 2006

In the presence of titanium(IV) chloride, 2-(dimethylamino)cyclobutanecarboxylic esters, equivalents of 1,4-zwitterions, reacted with carbonyl compounds to give δ-lactols or dihydropyrans.
Unusual Rotamer Equilibria in Solution and Atropisomerism in 9-(1,3-Dioxolan-2-y1)-1,2,3,4-tetraf1uorotriptycene
Authors: Yamamoto Gaku
Published: May 2006

The title compound exists as a 1:1 mixture of ap and ±sc rotamers at equilibrium in CDCl3. The origin of the unusually high population of the ap rotamer was explored by molecular mechanics calculations. The two rotamers were separately isolated as crystals by selective crystallization.
1,2-Migration of Perfluoroalkyl Groups in Anionotropic Rearrangement. The Acyloin Rearrangement of 4-Perfluoroalkyl-4-quinols
Authors: Uno Hidemitsu , Yayama Ayumi , Suzuki Hitomi
Published: May 2006

Treatment of 4-perfluoroalkyl-4-quinols with a catalytic amount of potassium t-butoxide gave 2-(perfluoroalkyl)hydroquinones or 5-perfluoroalkyl-2-cyclohexene-1,4-diones in good to moderate yields depending upon the substitution pattern of the quinols. Similarly, 2-hydroxy-3-methyl-2-perfluorooctyl-1-propyl-3-pyrrolin-5-one underwent the base-induced rearrangement to afford a perfluoroalkylated succinimide derivative.
Facile Preparation of Tetrabutylphosphonium Fluoride and Its HF Adducts. New Fluoride Anion Sources for Selective Nucleophilic Fluorination
Authors: Seto Hideharu , Qian Zhao-hui , Yoshioka Hirosuke , Uchibori Yukitaka , Umeno Masayuki
Published: May 2006

Anhydrous tetrabutylphosphonium hydrogen bifluoride (2), dihydrogen trifluoride prepared from aq. tetrabutylphosphonium hydroxide and aq. HF, and tetrabutylphosphonium fluoride prepared from 2 and BunLi were shown to be useful fluoride sources for selective nucleophilic fluorination of oxiranes, alkyl halides, alcohols and sulfonates of aliphatic and steroidal species.
Desing of the Catalyst for Partial Oxidation of Ethylene by Applying an Electrochemical Device
Authors: Otsuka Kiyoshi , Kobayashi Akihiko
Published: May 2006

The electrochemical device composed of the H3PO4-membrane on which various noble metals were attached, M/H3PO4/M′, was demonstrated as a probe of the catalysts for partial oxidation of C2H4. On the basis of the results, we have designed the catalyst (Pd–Ru–Graphite–H3PO4) for the selective synthesis of CH3CHO from C2H4.
Regioselective Synthesis and Polymerization of Substituted o-Trimethylsilylphenylacetylenes
Authors: Yamaguchi Masahiko , Tsukamoto Yukiharu , Ikeura Chinatsu , Nakamura Shigeo , Minami Toru
Published: May 2006

Substituted o-trimethylsilylphenylacetylenes were synthesized by o-metalation of phenylacetylenes with complex reagent of butyllithium and t-BuOK, and were polymerized in the presence of a tungsten catalyst giving deeply colored poly(arylacetylene)s. Relationship between the structure of monomers and polymers was examined.
Synthesis of Tetrakis(1,2-benzodithio)tetramethyleneethane Dication Salt and Its Two-electron Reduction
Authors: Sugimoto Toyonari , Kawachi Atsushi , Ikeda Kaoru , Yamauchi Jun
Published: May 2006

Tetrakis(1,2-benzodithio)tetramethyleneethane dication salt was obtained by two-electron oxidation of a head-to-head dimer of bis(1,2-benzodithio)allene. The dication was two-electron reduced at a comparatively low voltage into the corresponding diradical, whose ESR spectrum seemingly showed a fine structure. The characteristics of the diradical could not be obtained, since the signal intensity did not increase as a result of the preferential intramolecular radical coupling of the diradical into the original allene dimer.
Enantiodifferentiating Photoisomerization of 1,2-Diphenylcyclopropane Sensitized by Chiral Aromatic Esters
Authors: Inoue Yoshihisa , Shimoyama Hideo , Yamasaki Noritsugu , Tai Akira
Published: May 2006

Enantiodifferentiating cis-trans photoisomerization of 1,2-diphenylcyclopropane (1) in the presence of (−)-tetramenthyl 1,2,4,5-benzenetetracarboxylate as a chiral sensitizer gave (+)-(1S,2S)-1t in enantiomeric excesses (e.e.) of 10.4 and 2.8% in pentane and acetonitrile, respectively, while the photosensitization with the corresponding (−)-tetrabornyl ester afforded (+)-(1S,2S)-1t (3.8% e.e.) in pentane and, notably, the antipode (−)-(1R,2R)-1t (2.4% e.e.) in acetonitrile.
Diffusionless Electron Transfer of Xanthene Dyes in Nonpolar and Weakly Polar Donor- and Acceptor-Solvents
Authors: Kemnitz Klaus , Yoshihara Keitaro
Published: May 2006

Diffusionless electron transfer systems, comprised of excited xanthene dyes dissolved in nonpolar or weakly polar electron donor or acceptor, are distinguished by their direct access to the rate constant of electron transfer and by their potentiality for ultrafast electron transfer. We observed short fluorescence lifetimes of ≤ 6 ps for rhodamine 6G dissolved in p-benzoquinone, aniline and N,N-dimethylaniline.
Pig Liver Esterase-catalyzed Hydrolyses of Racemic Diacetates of Bicyclic Compounds and Interpretation of the Enantiomeric Specificity of PLE
Authors: Naemura Koichiro , Takahashi Nobuo , Ida Hirotsugu , Tanaka Shunsuke
Published: May 2006

Pig liver esterase-catalyzed hydrolyses of racemic diacetates of bicyclic compounds, bicyclo[2.2.1]heptanes, bicyclo[2.2.2]octanes, and bicyclo[3.2.1]octanes gave the optically active monoacetates and diacetates. The enantiomeric specificity of PLE toward diacetates of racemic diol substrates was analyzed by using the active site model.
Wavelength Dependence of Light-Induced Chemical Oscillation. Hexacyanoferrate(II)–Hydrogen Peroxide–Sulfuric Acid System
Authors: Mori Yoshihito , Srivastava Prem Kumar , Hanazaki Ichiro
Published: May 2006

We have measured the wavelength dependence of the light-induced chemical oscillation in the Fe(CN)64−–H2O2–H2SO4 system in a continuous-flow stirred tank reactor. The primary process for the induction of oscillation is suggested to be the photo-excitation of Fe(CN)63−.
Enantioselective Addition of Diethylzinc to Aldehydes Catalyzed by Chiral Hydroxy Aminal
Authors: Asami Masatoshi , Inoue Seiichi
Published: May 2006

Chiral secondary alcohols are obtained in high enantiomeric excesses (ee’s) by the enantioselective addition of diethylzinc to aldehydes in the presence of a chiral hydroxy aminal derived from (S)-2-(anilinomethyl)pyrrolidine.
Metal-ion-catalyzed Fluxionality of Pentadienyltins and Its Application to the Diels–Alder Reaction
Authors: Nishigaichi Yutaka , Takuwa Akio , Iihama Kenji , Yoshida Naofumi
Published: May 2006

(Z)-Pentadienyltins (PDT) as well as (Z)-allylic tins are isomerized to (E)-isomers most effectively by alkaline earth metal ions. The resulted (E)-PDT is trapped by 1,4-naphthoquinone to give the Diels–Alder adducts efficiently behaving as a reactive equivalent of 1,3-pentadiene.
New Addition Reactions of Cyclic Ethers with Esters and Thioesters Catalyzed by Quaternary Ammonium Salts or Crown Ether Complexes
Authors: Nishikubo Tadatomi , Sato Kazuya
Published: May 2006

A new addition reaction of 3-benzyloxymethyl-3-methyloxetane with S-phenyl thioacetate proceeded to give 3-benzyloxy-2-methyl-2-phenylthiomethylpropyl acetate catalyzed by 18-crown-6-potassium phenoxide complex. N-(2-Acetoxyethyl)-N-(2-phenoxyethyl)acetamide was also synthesized in high yield by the addition reaction of 5-methyl-4,6-dioxa-1-azabicyclo[3.3.0]octane with phenyl acetate, using tetrabutylammonium salts as catalysts.
Photoalkylation of α-Diketones with Tetraalkylstannanes via Electron Transfer
Authors: Kyushin Soichiro , Otani Shinju , Takahashi Tomoyuki , Nakadaira Yasuhiro , Ohashi Mamoru
Published: May 2006

Irradiation of α-diketones in the presence of tetraalkylstannanes gave α-ketols via electron transfer. The analogy between the photo-induced electron transfer reactions and mass spectrometry exists in the fragmentation of the radical cation of the stannanes.
Kinetic Evidence for the Existence of a Heterodinuclear Reaction Intermediate in the Mercury(II) Catalyzed Formation of Metalloporphyrins
Authors: Tabata Masaaki , Miyata Wakako
Published: May 2006

A reaction intermediate of a heterodinuclear metalloporphyrin involving mercury(II) and zinc(II) was kinetically observed as a two-step reaction pathway and confirmed by both the rate equation and the change in absorption spectra in the reaction of dimercury(II)porphyrin with aquazinc(II).
Some Kinetic Properties of Mixed Chain Alkylammonium Ion Vesicles
Authors: Fujita Tsunehisa , Moss Robert A
Published: May 2006

The relationship between lipid structure and lipid dynamics of bilayer covesicles derived from mixed chain dialkylammonium ion lipids was investigated.
Synthesis of Heteropolyoxometalate Pillared Layered Double Hydroxides via Calcined Zinc-Aluminium Oxide Precursors
Authors: Narita Eiichi , Kaviratna Padmananda , Pinnavaia Thomas J
Published: May 2006

An amorphous zinc-aluminium oxide solid solution, Zn0.67Al0.33O1.17, Prepared by the thermal decomposition of the acidic layered double hydroxide (LDH), [Zn0.67·Al0.33(OH)2](CO3)1.17·0.33H2O, was found to react with Keggin-like heteropolyoxometalate anions such as α-[Si·W11O39]8− and α-1,2,3-[SiV3W9O40]7− in acid solution to form pillared LDH structures with gallery heights of 9.9 Å.
Preparation of Oxidation Catalysts by Immobilization and Isolation of Metal Complexes into Monolayer Matrix on Silica Surface
Authors: Miki Keiji , Sato Yoshiki
Published: May 2006

Immobilization and isolation of cobalt-pyridine complexes in the fence of monolayer matrix on silica surface provided the active catalysts for oxidation of 1,2,3,4-tetrahydronaphthalene.
Electrochemical Approach to Germenium and Silicenium Ions
Authors: Okano Mitsutoshi , Mochida Kunio
Published: May 2006

The reduction potentials for carbonium, silicenium, and germenium ions were determined by cyclic voltammetry of neutral precursor compounds. The reduction potential shifted to the negative direction as the center element changed from C to Ge.
Palladium(0)-catalyzed Dimerization/Allylation of 1-Alkynes with Allyl Carbonate
Authors: Inoue Yoshio , Ohuchi Kunihiro , Kawamata Tadanori , Ishiyama Jun-ichi , Imaizumi Shin
Published: May 2006

Palladium(0) complexes catalyzed a dimerization/allylation of 1-alkynes with allyl carbonate in which three carbon-carbon bonds were formed regio- and stereoselectively.
Surface Reaction of Methyl Sulfonates on Alumina Studied by Inelastic Electron Tunneling Spectroscopy
Authors: Hida Atsushi , Higo Morihide , Kamata Satsuo
Published: May 2006

Vibrational spectra of methyl sulfonates adsorbed onto an alumina surface have been measured by inelastic electron tunneling spectroscopy. The spectra indicate that the sulfonates react with OH groups of the alumina surface and are adsorbed dissociatively onto the alumina surface as sulfonate ions.
Image Formation Due to Thermo-chemical Decoloration in Blue Colored Organopolysilane/Titanylphthalocyanine Layered Film Patterned by Ultra-violet Light
Authors: Kakui Mikio , Yokoyama Kenji , Yokoyama Masaaki
Published: May 2006

Blue colored poly(methylphenylsilane) (PhMeSi)x/titanylphthalocyanine (TiOPc) layered films have been found to suffer thermo-chemical decoloration effectively by ultra-violet (UV) light irradiation followed by heat treatment at temperature of 250 °C. The decoloration has been confirmed to result from chemical destruction of TiOPc, which is initiated by thermo-decomposition of organopolysilane, and particularly accelerated by UV irradiation. The present thermo-chemical decoloration can be applicable as a new image recording.
New Langmuir–Blodgett Films Based on Substituted 1,2-Dithiolium-TCNQ Radical Anion Salts
Authors: Gionis Vassilis , Ficket Odile , Izumi Mitsuru , Garrigou-Lagrange Chantal , Amiell Jacques , Papavasseliou Georges , Delhaes Pierre
Published: May 2006

Based upon the synthesis of 3,4,5-tris(alkylthio)-1,2-dithiolium cation salts, we have realized new Langmuir–Blodgett films. They present either a centrosymmetrical or noncentrosymmetrical bilayer organization depending on the involved molecular association with iodine, tetracyanoquinodimethane or some other radical anion.
Distribution Map of the Main Peak of Nickel K-Edge X-Ray Absorption Near Edge Structure. Situations of the Nickels in Hydrogenases in the Map
Authors: Yamamura Takeshi , Nakamura Nobuhumi , Yasui Atsushi , Sasaki Kenju , Arai Hiroki
Published: May 2006

Nickel K edge XANES spectra of 27 compounds were observed. Energy and normalized height mapping of their main peaks has shown a characteristic area for square planar geometry, especially for the cases containing sulfur back scatterer. The coordination geometries of the nickels in hydrogenases and CO dehydrogenases were discussed by using their published data.