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The synthesis, spectroscopic characterization, and single crystal X-ray structures of [(η5-C5Me4H)2Ga(μ2-NH2)] (1), [(η5-C5Me5)2Ga(μ2-NH2)]2 (2), [(η5-C5Me5)Ga(Cl)(μ2-NH2)]3 (4), [(η5-C5Me5)2Ga(μ2-N(H)Et)]2 (5) are described. Preliminary studies of the thermal and photochemical decomposition of compound 2 were performed to evaluate its suitability as single source precursors to GaN.

Decrements in cognitive function are common in cancer patients and other clinical populations. As direct neuropsychological testing is often not feasible or affordable, there is potential utility in screening for deficits that may warrant a more comprehensive neuropsychological assessment. Furthermore, some evidence suggests that perceived cognitive function (PCF) is independently associated with structural and functional changes on neuroimagery, and may precede more overt deficits. To appropriately measure PCF, one must understand its components and the underlying dimensional structure. The purpose of this study was to examine the dimensionality of PCF in people with cancer. The sample included 393 cancer patients from four clinical trials who completed a questionnaire consisting of the prioritized areas of concerns identified by patients and clinicians: self-reported mental acuity, concentration, memory, verbal fluency, and functional interference. Each area contained both negatively worded (i.e., deficit) and positively worded (i.e., capability) items. Data were analyzed by using Cronbach's alpha, item-total correlations, one-factor confirmatory factor analysis, and a bi-factor analysis model. Results indicated that perceived cognitive problem items are distinct from cognitive capability items, supporting a two-factor structure of PCF. Scoring of PCF based on these two factors should lead to improved assessment of PCF for people with cancer.

Silica nanowires are one-dimensional nanomaterials that are being developed for use in biological systems. Unfortunately, little is known regarding the cytotoxic potential of this type of nanomaterial. Here, using two different human epithelial cell lines we have examined the cytotoxicity of silica nanowires over a broad concentration range. The results indicate that silica nanowires are nontoxic at concentrations below 190 µg/ml but exhibit considerable cytotoxicity at higher concentrations. Examination of the mechanisms responsible for nanowire-induced cytotoxicity indicates that apoptotic pathways are not activated. Instead, cytotoxicity appears to be primarily due to increased necrosis in cells exposed to high concentrations of nanowires. In contrast to what was seen with silica nanowires, analysis of silica nanoparticles revealed very little cytotoxicity even at the highest concentrations tested. These results indicate that structural differences between silica nanomaterials can have dramatic effects...

In an effort to develop a general synthetic route to ansa-chromocene complexes with diverse ligand frameworks, we investigated ansa-magnesocene compounds as an alternative, potentially more versati...

The octamethylaluminocenium cation [Cp‘2Al]+ (Cp‘ = C5Me4H) was formed both by halide abstraction in the reaction between [Cp‘2AlCl]2 and AlCl3 and by cyclopentadienide abstraction in the reaction between Cp‘3Al and [CPh3][B(C6F5)]4. [Cp‘2Al]+ is less thermally stable than [Cp*2Al]+ (Cp* = C5Me5) but is more active as an initiator for isobutene polymerization. The X-ray crystal structures of [Cp‘2AlCl]2 and [Cp‘2Al][B(C6F5)4] are reported.

The ansa-aluminocene compound [Me4C2(C5H4)2Al-μ-Cl]2 (2) was prepared by reacting [Me4C2(η5-C5H4)2Mg] with AlCl3. Addition of THF and t-butyl isocyanide to 2 produced the corresponding monomeric Lewis base adducts [Me4C2(η5-C5H4)2Al(L)] (L = THF (3), t-BuNC (4)). X-ray crystal structure determinations revealed (η1,η5), (η1,η3), and (η1,η1) combinations of cyclopentadienyl ring hapticities for 2, 3, and 4, respectively. The solution structures and fluxional behavior of the compounds were characterized using a battery of dynamic and 2-D NMR techniques. Line shape analysis of variable temperature 1H and 13C{1H} NMR spectra of 2 in toluene-d8 yielded an activation barrier (Ea) of 8 kcal mol−1 for the dynamic averaging of proton and carbon environments of the bridged dicyclopentadienyl ligand framework. Circumambulatory migration of aluminum about its cyclopentadienyl rings could be ruled out as the source of this averaging. The cyclopentadienyl ring coordination modes that were identified in the solution spectra of 2 and 4 at slow exchange (η1,η1 and η2,η3, respectively) are considerably different from the ones found in the crystal structures of the compounds. Besides rearrangements in the bonding between aluminum and its cyclopentadienyl rings, there is another dynamic process, possibly inversion at aluminum, that leads to additional signal averaging in the 1H and 13C{1H} NMR spectra of compound 4.

Methylenetriphenylphosphorane was coordinated to the boron of phenylborylidene-bridged bis(cyclopentadienyl)- and bis(2-Me,4-Ph-indenyl)zirconium dichloride to form zwitterionic ansa-zirconocene complexes. The cyclopentadienyl complex 2, when activated with MAO, exhibits remarkable polymerization activity that is more than an order of magnitude greater than that of a related amidoborylidene-bridged complex as well as the commercially important precatalyst [Cp′−SiMe2−N−tBu]TiCl2 (Cp′ = C5Me4). The zwitterionic bis(2-Me,4-Ph-indenyl)zirconium dichloride species is isolated as a mixture of rac and meso isomers 4−6. The propylene polymerization efficiency of the isomer mixture activated by MAO is greater than that of a related silylene bridged system at 70 and 85 °C; however, the activity of the zwitterionic system decreased with further increase in temperature. The high level of isotactic triads (63.6%) and pentads (52.4%) in the polypropylene formed by 4−6 indicates that the rac isomer is the most active precatalyst of the mixture. The molecular structures of 2 and the rac bis-indenylzirconium isomer 4 and one of the meso isomers 5 are described. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Treatment side effects and decreased quality of life associated with androgen deprivation therapy (ADT) suggest the need for supportive services for prostate cancer (PC) patients receiving ADT. Nonetheless, uptake of services is low, suggesting that PC patients' preferences are not being addressed. We examined interest in supportive services and predictors of interest among 118 PC patients receiving ADT. Overall interest in services was associated with lower quality of life (p = 0.01). The majority of participants expressed interest in informational services (70%), with a minority (22%) expressing interest in psychosocial services. Interest in psychosocial services was associated with younger age (p = 0.02), and shorter duration of ADT (p < 0.04), but was unrelated to psychological distress or social support. Although most men (68%) reported that they would prefer not to take medication for depression, 75% would do so if advised by their physician. Overall, results suggest that PC patients on ADT prefer individualized informational support. Substantial interest (61%) in Oncolink, an internet-based informational resource, suggests the Internet may provide an acceptable mode of service delivery. Health care providers should consider integrating increased informational support into routine care and, more generally, consider patient preferences in prioritizing and designing support services.

The reductive coupling of guaiazulene with activated calcium in THF at 30–35 °C affords a 60:40 mixture of two isomers, 8,8′-(1) and 8,6′-(2) (diguaiazulenide)bis(tetrahydrofuran)calcium, respectively, in nearly quantitative yield. The isomers were separated and purified by recrystallization. The X-ray crystal structure of 1 is reported. A modest dependence of the isomer ratio on the reaction temperature was noticed. At lower temperature (9 °C) the 8,6′ isomer, 2, is favored slightly, and at higher temperature (67 °C) selectivity for the 8,8′ isomer, 1, is slightly enhanced. Thermolyses of each isomer revealed that 1 is the thermodynamically preferred isomer.

1. IntroductionSince the discovery of ferrocene [1] and the elucida-tion of its bis-pentahapto sandwich structure 50 yearsago [2], bis-cyclopentadienyl-transition metal and -lanthanide metal compounds have been central tosome of the most important developments in modernorganometallic chemistry. An odd, closed ligand in theDavies

The degree to which 6,6-dimethylfulvene, 6,6-diethylfulvene, and 6-cyclopentylidenefulvene form unbridged calcocenes in reductive coupling reactions with activated calcium were compared. The identification of alkenyl substituents along with alkyl substituents among the unbridged calcocenes confirms that hydrogen atom or proton transfer between dialkylfulvenes and their radical anions or dianions is responsible for the formation of unbridged calcocenes. The tendency to form unbridged calcocenes instead of ansa-calcocenes is higher for 6,6-diethylfulvene and 6-cyclopentylidenefulvene than for 6,6-dimethylfulvene. 1,1‘-Dicyclopentenylcalcocene, 1, which is formed in the reaction between cyclopentylidenefulvene and calcium, was purified and crystallographically characterized. Photolysis of 1 leads to [2+2] cyclization of the cyclopentenyl substituents to form 2, an ansa-calcocene with a tricyclo[3.3.0.0]decane-1,10-diyl bridge.

Boron-bridged group-4 ansa-metallocene complexes are newcomers to the field of metallocene-mediated olefin polymerization catalysis. Because of the Lewis acidity of the boron bridge, it is more reactive than the more common carbon and silicon bridges. It is also more vulnerable to cleavage from the ligand framework by nucleophilic agents. A primary goal of our work is to involve the boron bridge more actively in the reaction chemistry of the metallocene while keeping the bridge intact.

ansa-Calcocene compounds are effective reagents for the synthesis of ansa-chromocene complexes from CrCl{sub 2} in the presence of a trapping ligand such as carbon monoxide or an isonitrile. A variety of ansa-chromocene carbonyl and tert-butyl isocyanide complexes have been prepared in this manner in high yields. The X-ray crystal structure of one of these complexes, [trans-1,2-(3,4-(CH{sub 3}O){sub 2}C{sub 6}H{sub 3}){sub 2}C{sub 2}H{sub 2}{l_brace}{eta}{sup 5}-C{sub 5}H{sub 4}{r_brace}{sub 2}]CrCO, is described. Electrochemical studies on these complexes show that the isonitrile derivatives are more easily oxidized than the carbonyl derivatives. Preliminary examination of the reactivity of these complexes indicates that the nature of the substitution along the ethanediyl ansa-bridge influences the relative stabilities of the carbonyl complexes to oxidation in air, the ease with which the carbonyl ligands undergo substitution with tert-butyl isocyanide, and the relative sensitivities of the tert-butyl isocyanide adducts to photodecomposition. The ansa-bridge substitution also appears to influence the ability of the complexes to undergo structural changes, such as ring slippage, as revealed in their cyclic voltammograms.

An association between creativity and bipolar disorders has been noted among eminent creative individuals, and in clinical probands and their first degree relatives (e.g. Andreasen, 1987; Jamison, 1989; Richards, 1994). Those studies propose that a genetic liability for bipolar disorder carries with it an increased propensity for creative thought and action. The present study applied strict quantitative criteria to establish bipolar diathesis in order to determine whether the association between bipolarity and creativity would generalise to creative individuals beyond the circle of eminence in a nonclinical population. The Adjective Checklist Creative Personality Scale (ACL-CPS) and the revised General Behavior Inventory (GBI) were completed by 72 undergraduates. ACL-CPS scores were significantly elevated for students displaying periods of hypomania with no depression (hyperthymic), but not for those with alternating periods of hypomania and depression (cyclothymic) or predominantly depressed (dysthymic) ...

Cyclopentadienylaluminum compounds have been a curiosity due to the ring-slipped structures they exhibit and due to their highly fluxional nature, which has prevented the freezing out of discrete solution structures on the NMR time scale. Lately, increased attention toward these compounds in the form of molecular structure determinations, theoretical calculations, and 27Al-NMR spectroscopic measurements is providing a clearer picture of the bonding between the aluminum and its cyclopentadienyl ring(s). A variety of ring coordination geometries (η1, η2, η3, η5) have been identified in molecular structures of these compounds, and although theoretical calculations reveal very small energy differences between different haptotropes, consistent with their highly fluxional behavior in solution, there is close agreement between the calculated ground state geometries for the compounds and the geometries they exhibit in the solid state and in solution. Theory and experiment reveal a delicate balance of covalent π-interactions and ionic interactions between the aluminum and its cyclopentadienyl ring. Although the balance is easily tipped by steric effects, some structural trends are emerging. The solution 27Al-NMR chemical shifts of cyclopentadienylaluminum compounds are surprisingly diagnostic of their geometries, exhibiting a strong correlation with coordination numbers that take into account the hapticity of the cyclopentadienyl ring.

1-E-benzylidene-4,7-dimethylindene (1) is reductively coupled by activated calcium to form two isomers, trans-Ph2C2H2-rac-(η5-4,7-Me2−C9H4)2Ca(THF)2 (trans-rac-2) and cis-Ph2C2H2-meso-(η5-4,7-Me2−C9H4)2Ca(THF)2 (cis-meso-2) in an approximately 1:1 ratio. Reaction of the calcium species with FeCl2 produces a mixture of the corresponding trans-rac and cis-meso ferrocenophane species (3) along with another ferrocenophane isomer that is presumed to be either the trans-meso or cis-rac isomer. Thus, the relative geometry of the indenyl rings is not retained entirely during the transfer of the ligand framework from calcium to iron. A complete scrambling of the indenyl ring geometry appears to occur upon transfer of the ligand framework from calcium to zirconium. The results of X-ray crystal structure determinations of 1-E-benzylidene-4,7-dimethylindene, trans-Ph2C2H2-rac-(η5-4,7-Me2−C9H4)2Ca(THF)2, and trans-Ph2C2H2-rac-(η5-4,7-Me2−C9H4)2Fe are described.

cis-[(1,2-diphenyl-1,2-dicyclopentadienyl)ethanediyl]bis(tetrahydrofuran)calcium is prepared by reductively coupling phenylfulvene with activated calcium to produce cis and trans isomers which can be separately crystallized. The cis isomer crystallizes in the monoclinic space group P21/c. The cell parameters are: a = 9.7006(1), b = 18.9839(1), c = 14.2018(2) A, β = 91.263(1)°, V = 2614.70(5) A3, D calc = 1.252 mg/m3, and Z = 4. Spectroscopic and crystallographic data for the cis-isomer are presented and discussed.

Reductive coupling of dimethylfulvene with alkaline earth metals yields inseparable mixtures of the tetramethylethylene-bridged complex Me4C2(C5H4)2M and the unbridged metallocene (i-PrCp)2M (M = M...

The syntheses and X-ray crystal structures of the boron-bridged ansa-metallocene complexes [{Ph(Me2S)B(η5-C5H4)2}ZrCl2]·C6D6 (2) and [{Ph(Me3P)B(η5-C5H4)2}ZrCl2] (3) are reported. Complex 2 is obtained as the product of a double dehalodesilylation reaction between PhB(C5H4SiMe3)2 and ZrCl4(SMe2)2. The dimethyl sulfide adduct of 2 is readily replaced with trimethylphosphine to afford 3. Efforts to alkylate 2 were unsuccessful, presumably due to the lability of the dimethyl sulfide and, hence, its inability to protect the boron bridge from nucleophilic attack by alkyl anions. In contrast, the trimethylphosphine adduct in 3 binds tightly enough to the boron bridge to protect it from nucleophilic attack. Also, unlike 2, complex 3 is activated by methylalumoxane toward the polymerization of ethylene.

X-ray crystallographic studies, low-temperature 1H and 13C NMR studies, and 27Al NMR studies of a series of homoleptic tricyclopentadienylaluminum compounds [(C5H5)3Al (1), (MeC5H4)3Al (2), (1,2,4-Me3C5H2)3Al (3), (1,2,3,4-Me4C5H)3Al (4)] are reported along with ab initio calculations on model cyclopentadienylaluminum compounds. The ring-coordination geometries exhibited by the tricyclopentadienylaluminum compounds in the solid state vary with the number of methyl substituents on the cyclopentadienyl rings. The X-ray crystal structure of compound 1 revealed two unique molecules in the unit cell, one with an {η2, η1.5, η1.5} combination of ring geometries and the other with an {η2, η1.5, η1} combination of ring-coordination geometries. In the crystal structure of compound 3, one cyclopentadienyl ring is coordinated η5 to the aluminum while the other two rings are η1. Compound 4 exhibits monohapto coordination of all three tetramethyl-substituted cyclopentadienyl rings in the solid state. These compounds ar...

A new series of half-sandwich (borylcyclopentadienyl)titanium trichloride complexes have been prepared which include the boryl substituents [1,2-(C6H4O2)]B−, Ph(Cl)B−, Ph2B− and a (PhB

which results from the double insertion of the isonitrile at a single Al-cyclopentadienyl ring position. Double isonitrile insertion occurs in preference to a single insertion such that only unreacted Cp3′Al and the title compound are observed when fewer than two equivalents of the isonitrile are consumed. The molecular structure of has been determined by single-crystal X-ray diffraction. The aluminum center is tetracoodinate with two η1-cyclopentadienyl rings and the coupled isonitrile fragment bonding through a carbon of one iminoacyl group and a nitrogen of the other to form a four-membered azametallacycle.

126 Background: Comorbidities and treatment-related symptoms (sx) affect overall function and may impact return to work. We evaluated SF-12 physical and mental functioning in CRC working (W) and non-working (NW) survivors. Methods: 300 Stage I-III CRC survivors age 25-70 years identified by PA Cancer Registry who completed curative therapy 3-5 years prior to study and were employed at diagnosis were surveyed with validated measures via mail-survey procedures. Current work status (working/not working), demographics, and medical factors (diagnosis, treatment, comorbidities) were assessed, as was fatigue, insomnia, distress, cognitive sx, neuropathy, bowel sx, and urinary sx. Study approved by PA Department of Health; participants (pts) provided informed consent. Results: Pts average age 57 yrs (80% < 65 yrs), 56% male, 87% white, 67% educated beyond high school, 73% married. 56% had rectal cancer, 51% had chemotherapy, 39% had radiation therapy, 16% had an ostomy. Work status at survey: 226 pts (75%) W; 74 pts (25%) NW. Higher comorbidity number was associated with lower physical (PCS) component scores in both W and NW groups (p = 0.004 and 0.013), and with lower mental (MCS) component scores in the NW group (p = 0.004). Among W pts, predictors of lower PCS were fatigue (p = 0.001), bowel problems (p < 0.001), neuropathy (p = 0.009), and being male (p = 0.03). Predictors of lower MCS were fatigue (p = 0.003), cognitive issues (p < 0.001), and distress (p < 0.001). Among NW pts, predictors of lower PCS were fatigue (p = 0.02), neuropathy (p = 0.007), ostomy presence (p = 0.015), and being unmarried (p = 0.007). Predictors of lower MCS were distress (p < 0.001) and younger age (p = 0.007). Conclusions: Both W and NW CRC survivors have significant comorbidity and sx burden associated with poorer physical and mental functioning. Fatigue, neuropathy, and distress were predictors in both groups, while cognitive and bowel sx predicted poorer function among W survivors. Intervening on these modifiable sx may increase survivors’ return to work and improve functioning for those who do. Next steps will focus on intensive management of modifiable sx to determine the effect on physical and mental functioning and potential for returning to work after treatment.

Protonation of the metal occurs upon reaction of Me4C2(C5H4)2CrCO with [H(Et2O)2][B(3,5-(CF3)2C6H3)4] at −70 °C in thf-d8. The diamagnetic Cr(IV) hydride intermediate was characterized by 1H NMR spectroscopy. Its decomposition to a paramagnetic product mixture upon warming to room temperature is accompanied by the evolution of 0.5 equiv of gas that is 54% H2 and 46% CO. Crystals of the borate salt of the 17e- ansa-chromocenium carbonyl cation [Me4C2(C2H4)2CrCO]+ were isolated from the product mixture for a molecular structure determination.

The title compound, rac-[Ca(C24H12)(C4H8O)2], was synthesized using activated calcium and the neutral ligand in the presence of THF. Both enantiomers are present in the asymmetric unit. The Ca atom is in a distorted pseudo-tetrahedral four-coordinate environment with the following range of bond distances and angles (Cp = cyclo­penta­dienyl centroid): Cp—Ca 2.347 (4)–2.446 (4) A, Ca—O 2.346 (4)–2.357 (4) A, Cp—Ca—Cp 118.8 (2)–119.1 (2)° and O—Ca—O 87.39 (14)–87.93 (13)°.

Cyclopentadienylaluminum compounds have been a curiosity due to the ring-slipped structures they exhibit and due to their highly fluxional nature, which has prevented the freezing out of discrete solution structures on the NMR time scale. Lately, increased attention toward these compounds in the form of molecular structure determinations, theoretical calculations, and 27Al-NMR spectroscopic measurements is providing a clearer picture of the bonding between the aluminum and its cyclopentadienyl ring(s). A variety of ring coordination geometries (η1, η2, η3, η5) have been identified in molecular structures of these compounds, and although theoretical calculations reveal very small energy differences between different haptotropes, consistent with their highly fluxional behavior in solution, there is close agreement between the calculated ground state geometries for the compounds and the geometries they exhibit in the solid state and in solution. Theory and experiment reveal a delicate balance of covalent π-interactions and ionic interactions between the aluminum and its cyclopentadienyl ring. Although the balance is easily tipped by steric effects, some structural trends are emerging. The solution 27Al-NMR chemical shifts of cyclopentadienylaluminum compounds are surprisingly diagnostic of their geometries, exhibiting a strong correlation with coordination numbers that take into account the hapticity of the cyclopentadienyl ring.

Silica-based nanomaterials show promise for biomedical applications such as cell-selective drug delivery and bioimaging. They are easily functionalized, which allows for the conjugation or encapsulation of important biomolecules. Although recent in vitro studies suggested that silica-derived nanomaterials are nontoxic, in vivo studies of silica nanomaterial toxicity have not been performed. Using the embryonic zebrafish as a model system, we show that silica nanomaterials with aspect ratios greater than 1 are highly toxic (LD 50 = 110 pg/g embryo) and cause embryo deformities, whereas silica nanomaterials with an aspect ratio of 1 are neither toxic nor teratogenic at the same concentrations. Silica nanowires also interfere with neurulation and disrupt expression of sonic hedgehog , which encodes a key midline signaling factor. Our results demonstrate the need for further testing of nanomaterials before they can be used as platforms for drug delivery. From the Clinical Editor Silica-based nanomaterials show promise for biomedical applications such as cell-selective drug delivery and bioimaging. Using an embryonic zebrafish model system silica nanomaterials with aspect ratios greater than one were found to be highly toxic; whereas silica nanomaterials with an aspect ratio of one are neither toxic nor teratogenic. These results demonstrate the need for testing "nanomaterials" before they can be used as platforms for drug delivery.

The title complexes are stable, borate-bridged ansa-zirconocene species which have been prepared by reacting [{Ph(SMe2)B(η5-C5H4)2}ZrCl2] (1) with Cp*2AlMe and [PPN]Cl. Their molecular structures were determined by X-ray diffraction. Noteworthy are the stabilities of the borate−cyclopentadienyl linkages and the enhanced Lewis acidity of the boron within its strained ansa position.

A rare example of an unsubstituted hydrazido(1-) complex, Cp{sup *}{sub 2}ScN(H)NH{sub 2} (Cp{sup *} = ({eta}{sup 5}-C{sub 5}Me{sub 5})), prepared by reaction of 1 equiv of anhydrous hydrazine with Cp{sup *}{sub 2}ScCH{sub 3}, reacts with acetonitrile to form Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNH{sub 2}. The crystal structure of the complex is reported and reveals a five-membered, nearly planar (ScN(H)C(CH{sub 3})NNH{sub 2}) ring. The results of a labeling study using {sup 15}N{triple bond}CCH{sub 3} are consistent with a mechanism involving insertion of acetonitrile into the Sc-N bond of Cp{sup *}{sub 2}ScNHNH{sub 2}, followed by tautomerization to form Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNH{sub 2}. The closely related compounds Cp{sup *}{sub 2}ScN(H)NMe{sub 2} and Cp{sup *}{sub 2}ScN(H)C(CH{sub 3})NNMe{sub 2} also have been prepared by using an analogous reaction pathway, and the structure of the latter has been determined as well, revealing a four-membered, nearly planar (ScN(H)C(CH{sub 3})N(NMe{sub 2})) ring. 18 refs., 3 figs., 5 tabs.

Ternary clusters Cu(9)In(10)S(9)(SEt)(21)(PPh(3))(3) and Cu(11)In(6)S(7)(S(t)Bu)(15) were isolated from the UV-photolysis products of precursors (PPh(3))(2)CuIn(SEt)(4) and (PPh(3))(2)CuIn(S(t)Bu)(4), respectively, and structurally characterized.

The Facing Our Risk of Cancer Empowered (FORCE) website is devoted to women at risk for hereditary breast and ovarian cancers. One of the most frequently discussed topics on the archived messaged board has been prophylactic mastectomy (PM) for women with a BRCA1/2 mutation. We reviewed the messages, over a 4 year period, of 21 high risk women and their “conversational” partners who originally posted on a thread about genetic testing, genetic counseling and family history. We used a qualitative research inductive process involving close reading, coding and identification of recurrent patterns, relationships and processes in the data. The women sought emotional support, specific experiential knowledge and information from each other. They frequently found revealing their post PM status problematic because of possible negative reactions and adopted self-protective strategies of evasion and concealment outside of their web-based community. The FORCE message board was considered to be a safe place in which the women could be truthful about their choices and feelings. Results are discussed in terms of Goffman’s concepts “stigma” and “disclosure” and Charmaz’s concepts “interruptions,” “intrusions” and a “dreaded future.”

The Facing Our Risk of Cancer Empowered (FORCE) website is devoted to women at risk for hereditary breast and ovarian cancers (HBOC). To understand the unique health concerns and emotional support needs of these women, we examined threads on the FORCE archived message boards with relevance to the broader HBOC community. We report on a thread discussing the controversial decision to use hormone replacement therapy (HRT) following prophylactic oophorectomy (PO). We used a qualitative research inductive process involving close reading, coding and identification of recurrent patterns, relationships and processes in the data. Twenty-nine women posted 177 messages over 7 months. Two main groups of women posted: (1) Women who were BRCA+, had completed PO, and were debating or adjusting their HRT options in terms of optimizing both quality and quantity of life. (2) Women who were BRCA+, were contemplating PO, but wanted to better understand the potential physical and psychological consequences of surgical menopause before deciding. Frustrated by physicians' lack of knowledge and contradictory media articles about the long-term consequences of HRT in BRCA+ women, they sought resources, emotional support and specific experiential knowledge from each other and generated a unique sense of community and a high level of trust. Copyright © 2007 John Wiley & Sons, Ltd.

A detailed study of the thermal decomposition of the zwitterionic, ring-borylated ansa-chromocene hydrido carbonyl complex [Cr(CO)H{Me(4)C(2)(C(5)H(4))[C(5)H(3)B(C(6)F(5))(3)]}] (2) is described. This complex is formed in the reaction between [Cr(CO){Me(4)C(2)(C(5)H(4))(2)}] (1) and B(C(6)F(5))(3) in toluene at -78 degrees C. Above -25 degrees C, 2 decomposes to a 50:50 mixture of the low-spin, 17e Cr(III) complexes [Cr(CO){Me(4)C(2)(C(5)H(4))[C(5)H(3)B(C(6)F(5))(3)]}] (3b) and [Cr(CO){Me(4)C(2)(C(5)H(4))(2)}][HB(C(6)F(5))(3)] (4). Carbon monoxide elimination from 3 b generates high-spin, 15 e [Cr{Me(4)C(2)(C(5)H(4))[C(5)H(3)B(C(6)F(5))(3)]}] (3a), which coordinates two other electron-donating ligands, such as xylyl isocyanide, PMe3, and PPh(2)Me to form the low-spin, 17 e electron complexes 3c, 3d, and 3e, respectively. High-spin, 15 e [Cr{Me(4)C(2)(C(5)H(4))(2)}][HB(C(6)F(5))(3)] (5) is generated by heating 3 b in toluene at 100 degrees C and periodically removing the evolved CO. Efforts to isolate more than a few X-ray quality crystals of 5 were thwarted by its tendency to form an insoluble precipitate (6) with the same molecular formula. Heating the solution of 5 at 120 degrees C results in its partial conversion (ca. 28 %) to 3a, thereby allowing the formation of 3a in yields as high as 74 % from the reaction between 1 and B(C(6)F(5))(3). The X-ray crystal structures of 3 b-e and 5 are described. Cyclic voltammetry measurements on 3 a-e reveal a dramatic reduction in the redox potentials of the complexes relative to their non-borylated analogues. DFT calculations show that this is due primarily to electrostatic stabilization of the oxidized species by the negatively charged borylate group. EPR and 19F NMR spectroscopy allow 3a to be distinguished from its Lewis base adducts 3 b-e and reveal the relative affinities of different Lewis bases for the chromium.

The synthesis and characterization of ultrafine CuInS2 nanoparticles are described. Ultraviolet irradiation was used to decompose a molecular single source precursor, yielding organic soluble approximately 2 nm sized nanoparticles with a narrow size distribution. UV-vis absorption, 1H and 31P{1H} NMR, and fluorescence spectroscopies and mass spectrometry were used to characterize decomposition of the precursors and nanoparticle formation. The nanoparticles were characterized by high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy energy dispersive X-ray spectroscopy, powder X-ray diffraction (XRD), electron diffraction, inductively coupled plasma analysis, UV-vis absorption spectroscopy, and fluorescence spectroscopy. They have a wurzite-type crystal structure with a copper-rich composition. The hypsochromic shift in their emission band due to quantum confinement effects is consistent with the size of the nanocrystals indicated in the HRTEM and XRD analyses.

A variety of 18e ansa-chromocene isocyanide complexes were prepared via ligand substitution on the carbonyl complexes. The relative π-accepting character of the different isocyanide ligands was eva...

This project proposed to develop, implement, and evaluate a peer-staffed toll-free hotline for individuals at high risk of developing hereditary breast cancer, either through family history or known BRCA1/2 mutations. The project is designed to demonstrate the acceptability and effectiveness of this tool for meeting the needs of these individuals and their families, and documents the range of problems for which assistance is sought. We have designed and implemented a refined peer counselor protocol that can be disseminated in larger multiple component peer-support packages. The Helpline Manual and Resource Guide was completed and distributed to our volunteers as part of an intensive training program. We successfully established the hotline, now called The Penn/F.O.R.C.E Telephone Helpline for individuals Concerned about Hereditary Breast and Ovarian Cancer," and opened the phone lines to the public on December 2, 2003. To date caller response to this service has been enthusiastically positive and has resulted in uptake of referrals to genetic counselors and gynecologic oncologists. Our counselors have addressed both psychosocial and practical issues associated with knowledge of mutation status, anxiety about personal and familial risk, communications difficulties with family and health professionals, concerns about discrimination, and difficulties accessing appropriate medical and support services.

Animal models and naturalistic studies of androgen decline in aging men suggest that low testosterone levels contribute to cognitive difficulties. Suppression of testosterone by androgen deprivation therapy (ADT) is the preferred treatment for advanced prostate cancer (PC) and in recent years has been increasingly prescribed for treatment of early stage PC. Although many of the side effects of ADT are well documented, potential cognitive impairment associated with ADT has been neglected in the literature. Our preexisting data indicate that 35% of men receiving ADT report moderate to sever difficulties with attention, concentration, and memory. In addition to normal age-related declines in cognitive function, men receiving ADT may experience hormone-related cognitive impairments that remain undetected and untreated. This study describes the nature and prevalence of objectively assessed cognitive difficulties in PC patients treated with ADT, examines the relationship between subjective reports of cognitive impairment and objective measurement of cognitive performance, and assesses relationships among fatigue, psychological distress, and cognitive function. Preliminary results show that 58% of the men have cognitive deficits greater than or equal to 1 SD below age- and education-adjusted population norms in one or more cognitive domains, and 92% have at least one area of performance greater than or equal to 1 SD below expected functioning based on estimated premorbid IQ.

The first thermally robust and air stable bent-sandwich chromocene complex with chromium in the +4 oxidation state has been isolated and fully characterized.