Di-chlorido-(η6-p-cymene)[tris-(4-meth-oxy-phen-yl)phosphane]ruthenium(II).

The title compound, [RuCl2(C10H14)(C21H21O3P)], crystallizes with two complex mol-ecules in the asymmetric unit. The RuII atom has a classical three-legged piano-stool environment being coordinated by a cymene ligand [Ru-centroid = 1.707 (2)/1.704 (2) Å], a tris-(4-meth-oxy-phen-yl)phosphane ligand [Ru-P = 2.3629 (15)/2.3665 (15) Å] and two chloride atoms with the Ru-Cl bonds adopting two distinct values of 2.4068 (16)/2.4167 (16) and 2.4016 (15)/2.4244 (16) Å. The effective cone and solid angles for the phosphane ligands were calculated to be 149.5/150.2° and 25.3/25.6°, respectively. In the crystal, weak C-H⋯Cl/O/π inter-actions are observed. The crystal was refined as a two-component twin.

Steric and electronic evaluations of P(o-tol)R2, where R is phenyl or cyclohexyl: crystal structures of SeP(o-tol)R2.

The crystal structures of SeP(o-tol)R2, where o-tol is ortho-tolyl (2-methylphenyl) and R is Ph (phenyl), namely (2-methylphenyl)diphenylphosphane selenide, C19H17PSe, or Cy (cyclohexyl), namely dicyclohexyl(2-methylphenyl)phosphane selenide, C19H29PSe, were determined to aid in the evaluation of the steric and electronic behaviour of these analogous phosphane compounds. The compounds crystallized in similar monoclinic crystal systems, but are differentiated in their unit cells by a doubling of the number of independent molecules for R = Cy (Z' = 2) and the choice of glide plane by convention. The preferred orientation for the o-tolyl substituent obtained from the X-ray structural analysis is gauche for R = Ph and anti for R = Cy (using the Se-P-Cipso-Cortho torsion angles as reference). Density functional theory (DFT) calculations showed both conformations to be equally probable and indicate that the preferred solid-state conformer is probably due to the minimization of repulsion energies, resulting in a packing arrangement primarily featuring weak C-H...Se interactions and additional C-H...π interactions in the R = Ph structure. A detailed electronic and steric analysis was conducted on both phosphanes using Se-P bond lengths, multinuclear NMR 1JSe-P coupling constants, theoretical topological evaluation and crystallographic and solid-angle calculations, and compared to selected literature examples. The results indicate that the use of the o-tolyl substituent increases both the electron-donating capability and the steric size, but is also dependent on whether the o-tolyl group adopts a gauche or anti conformation. The single-crystal geometrical data are unable to detect electronic differences between these two structures due to the somewhat large displacement parameters observed for the Se atom in the R = Cy structure.

The RNA-Binding Protein HuR Posttranscriptionally Regulates IL-2 Homeostasis and CD4+ Th2 Differentiation.

Posttranscriptional gene regulation by RNA-binding proteins, such as HuR (elavl1), fine-tune gene expression in T cells, leading to powerful effects on immune responses. HuR can stabilize target mRNAs and/or promote translation by interacting with their 3' untranslated region adenylate and uridylate-rich elements. It was previously demonstrated that HuR facilitates Th2 cytokine expression by mRNA stabilization. However, its effects upon IL-2 homeostasis and CD4+ Th2 differentiation are not as well understood. We found that optimal translation of Il2ra (CD25) required interaction of its mRNA with HuR. Conditional HuR knockout in CD4+ T cells resulted in loss of IL-2 homeostasis and defects in JAK-STAT signaling, Th2 differentiation, and cytokine production. HuR-knockout CD4+ T cells from OVA-immunized mice also failed to proliferate in response to Ag. These results demonstrate that HuR plays a pivotal role in maintaining normal IL-2 homeostasis and initiating CD4+ Th2 differentiation.

Chlorido{N-[2-(diphenyl-phosphan-yl)benzyl-idene]-2,6-diisopropyl-aniline-κP}gold(I) chloro-form 0.25-solvate.

The asymmetric unit of the title compound, [AuCl(C31H32NP)]·0.25CHCl3, contains two independent complex mol-ecules and half a chloro-form solvent mol-ecule, which is disordered across an inversion center. The Au(I) ions are each coordinated in a slightly distorted linear environment, with P-Au-Cl angles of 177.20 (4) and 178.54 (4)°.

Chlorido{[(E)-2-(diphenyl-phosphan-yl)benzyl-idene](furan-2-ylmeth-yl)amine-κP}gold(I).

In the title complex, [AuCl(C24H20NOP)], the ligand has N, P and O electron-donating atoms but the Au(I) atom is coordinated only by the 'soft' P atom and an additional Cl atom in an almost linear fashion. Important geometrical parameters include Au-P = 2.2321 (13) Å, Au-Cl = 2.2820 (13) Šand P-Au-Cl = 176.49 (5)°. The furan ring is disordered over two positions in a 0.51 (2):0.49 (2) ratio.

Access to musculoskeletal specialists and resources in free and charitable clinics: a survey of clinic directors.

OBJECTIVE: To evaluate the capabilities and resources of free and charitable clinics in the United States to deliver musculoskeletal care to an indigent population. DESIGN: A voluntary, anonymous, cross-sectional survey. SETTING: Electronic mailing list for the National Association of Free and Charitable Clinics in September 2011, and in person at the Annual Summit for the National Association of Free and Charitable Clinics in October 2011. At the time of survey, 427 member-clinics were eligible for participation. PARTICIPANTS: One hundred forty-five (34%) respondents were included in data analysis. INTERVENTIONS: None. MAIN OUTCOME MEASURES: Answers to a questionnaire regarding access to musculoskeletal care. RESULTS: The average annual clinic volume was 5690 patient visits. Low back pain was the most common orthopedic complaint. Access to musculoskeletal specialty consultants was rated as poor or worse in 83% of clinics surveyed. The majority of respondents (63%) believed that their staff was able to treat only half or fewer of the patients who presented with musculoskeletal complaints in their clinic. The resource most needed to treat these conditions was musculoskeletal physician consultants. CONCLUSIONS: Indigent populations have a strong need for musculoskeletal care, but affordable access to physiatrists and other musculoskeletal specialists is extremely limited. Personnel at surveyed clinics believed that the greatest need to improve care is better access to these specialty physicians.

(η(6)-Benzene)-(benzyl-diphenyl-phos-phane)dichloridoruthenium(II).

In the title compound, [RuCl(2)(C(6)H(6))(C(19)H(17)P)], the Ru(II) atom has a distorted pseudo-octa-hedral coordination environment with the metrical parameters around the metallic core as Ru-centroid(η(6)-benzene) = 1.6894 (11) Å, Ru-P = 2.3466 (6), Ru-Cl(avg.) = 2.4127 (7) Å; Cl-Ru-Cl = 88.07 (2) and Cl-Ru-P = 82.77 (2), 87.65 (2)°. The effective cone angle for the benzyl-diphenyl-phosphane was calculated to be 143°. In the crystal C-H⋯Cl and C-H⋯π inter-actions are observed.

(Acetyl-acetonato-κ(2)O,O')carbon-yl[dicyclo-hex-yl(2,6-diisopropyl-phen-yl)phosphane-κP]rhodium(I).

In the title compound, [Rh(C(5)H(7)O(2)){C(12)H(17)P(C(6)H(11))(2)}(CO)], the Rh(I) atom is coordinated by one carbonyl C, one P and two O atoms, forming a slighlty distorted square-planar configuration.

(Acetyl-acetonato-κ(2)O,O')[(2-bromo-phen-yl)diphenyl-phosphane-κP]carbonyl-rhodium(I).

In the title compound, [Rh(C(5)H(7)O(2))(C(18)H(14)BrP)(CO)], the Rh(I) atom adopts a slightly distorted square-planar geometry involving two O atoms [Rh-O = 2.077 (2) and 2.033 (2) Å] of the acetyl-acetonate ligand, one carbonyl C atom [Rh-C = 1.813 (2) Å] and one P atom [Rh-P = 2.242 (5) Å] of the PPh(2)(2-BrC(6)H(4)) phosphane ligand. Difference electron density maps indicate a disorder of the Br atom over two positions in an approximate 0.95:0.05 ratio. However, this disorder could not be resolved satisfactorily with the present data.

A review of verbal order policies in acute care hospitals.

BACKGROUND: Although verbal and telephone orders (VOs) are commonly used in the patient care process, there has been little examination of the strategies and tactics used to ensure their appropriate use or how to ensure that they are accurately communicated, correctly understood, initially documented, and subsequently transcribed into the medical record and ultimately carried out as intended. A systematic review was conducted of hospital verbal and telephone order policies in acute care settings. METHODS: A stratified random sample of hospital verbal and telephone order policy documents were abstracted from critical access, rural, rural referral, and urban hospitals located in Iowa and Missouri and from academic medical centers from across the United States. FINDINGS: Substantial differences were found across 40 acute care settings in terms of who is authorized to give (including nonlicensed personnel) and take VOs and in terms of time allowed for the prescriber to cosign the VO. When a nonphysician or other licensed prescriber was allowed to communicate VOs, there was no discussion of the process to review the VO before it was communicated in turn to the hospital personnel receiving the order. Policies within several of the same hospitals were inconsistent in terms of the periods specified for prescriber cosignature. Few hospitals required authentication of the identity of the person making telephone VOs, nor the use of practices to improve communication reliability. CONCLUSION: Careful review and updating of hospital VO policies is necessary to ensure that they are internally consistent and optimize patient safety. The implementation of computerized medical records and ordering systems can reduce but not eliminate the need for VOs.

(η(6)-Benzene)-dichlorido(dicyclo-hexyl-phenyl-phosphane)ruthenium(II) benzene sesquisolvate.

The asymmetric unit of the title compound, [RuCl2(C6H6)(C18H27P)]·1.5C6H6, contains one mol-ecule of the Ru(II) complex and one and a half solvent molecules as one of these is located about a centre of inversion. The Ru(II) atom has a classical three-legged piano-stool environment being coordinated by an η(6)-benzene ligand [Ru-centroid = 1.6964 (6) Å], two chloride ligands with an average Ru-Cl bond length of 2.4138 (3) Šand a dicyclo-hexyl-phenyl-phosphane ligand [Ru-P = 2.3786 (3) Å]. The effective cone angle for the phosphane was calculated to be 158°. In the crystal, weak C-H⋯Cl hydrogen bonds link the Ru(II) complexes into centrosymmetric dimers. The crystal packing exhibits intra- and inter-molecular C-H⋯π inter-actions resulting in a zigzag pattern in the [101] direction.

trans-Dichloridobis{tris-[4-(trifluoro-methyl)phen-yl]phosphane-κP}palla-dium(II) dichloro-methane monosolvate.

The title compound, [PdCl2(C21H12F9P)2]·CH2Cl2, crystallizes with two independent complex molecules (each having the Pd(II) atom situated on an inversion centre) and a dichloro-methane molecule in the asymmetric unit. The independent Pd(II) atoms are in perfectly linear orientations of the ligands in mutually trans positions, but distortions of the Cl-Pd-P angles ranging from 86.151 (19) to 93.849 (19)° are evident. The effective cone angles for the tris-[4-(trifluoro-meth-yl)phen-yl]phosphane ligand were calculated to be 159 and 161°. In the crystal, weak C-H⋯Cl/F inter-actions create a three-dimensional supramolecular network. Loose packing at two of the -CF3 groups resulted in large thermal vibrations which were treated as two-component disorders [occupancy ratios 0.50:0.50 and 0.628 (15):0.372 (15)].

trans-Dichloridobis{dicyclo-hex-yl[4-(dimethyl-amino)-phen-yl]phosphane-κP}platinum(II) dichloro-methane disolvate.

In the title complex, trans-[PtCl2{P(C6H11)2(4-Me2NC6H4)}2]·2CH2Cl2, the Pt(II) atom is located on an inversion centre, resulting in a trans-square-planar geometry. Important geometric parameters are the Pt-P and Pt-Cl bond lengths of 2.3258 (6) and 2.3106 (6) Å, respectively, and the P-Pt-Cl angles of 89.64 (2) and 90.36 (2)°. The effective cone angle for the dicyclo-hex-yl[4-(dimethyl-amino)-phen-yl]phosphane unit was calculated to be 164°. The compound crystallizes with two dichloro-methane solvent mol-ecules; one of which is severely disordered and was treated using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155].

trans-Di-µ-chlorido-bis-{chlorido[tris-(3,5-dimethyl-phen-yl)phosphane-κP]palla-dium(II)} dichloro-methane monosolvate.

In the dimeric title compound, [Pd2Cl4{P(C8H9)3}2]·CH2Cl2, the metal complex molecule is situated about an inversion centre and is accompanied by a dichloro-methane solvent mol-ecule situated on a twofold rotation axis. The Pd(II) atom has a slightly distorted square-planar coordination sphere. The effective cone angle for the tris-(3,5-dimethyl-phen-yl)phos-phane ligand was calculated to be 169°. In the crystal, the metal complex and solvent mol-ecules are linked via C-H⋯Cl inter-actions, generating chains along [10-2]. There are also C-H⋯π and weak π-π inter-actions present [centroid-centroid distance = 3.990 (2) Å, plane-plane distance = 3.6352 (15) Šand ring slippage = 1.644 Å], forming of a three-dimensional structure.

Di-µ-chlorido-bis-({8-[bis-(naphthalen-1-yl)phosphan-yl]naphthalen-1-yl-κ(2) C (1),P}palladium(II)) dichloro-methane disolvate.

The title compound, [Pd2{P(C10H7)2(C10H6)}2Cl2]·2CH2Cl2, shows cyclo-metalation of one naphthalen-1-yl substituent of each of the phosphane ligands to the Pd dimer in a trans orientation; the complete dimer is generated by a centre of inversion. Two dichloro-methane solvent mol-ecules create C-H⋯Cl inter-actions with the metal complex, generating supermolecular layers in the ab plane. Additional C-H⋯π and π-π [centroid-centroid distances = 3.713 (3), 3.850 (4) and 3.926 (3) Å] inter-actions join these planes into a three-dimensional supermolecular network.

Tris(naphthalen-1-yl)phosphane chloro-form hemisolvate.

The title compound, P(C10H7)3·0.5CHCl3, was isolated after the unsuccessful reaction of KSeCN and tris-(naphthalen-1-yl)phosphane. The solvent mol-ecule is disordered about an inversion center. The effective cone angle of the phosphine is 203°. In the crystal, weak C-H⋯Cl and C-H⋯π inter-actions are observed.

Diphenyl(pyridin-2-yl)-phosphane selenide.

In the title compound, C(17)H(14)NPSe, the P atom has a distorted tetra-hedral environment resulting in an effective cone angle of 163°. In the crystal, C-H⋯Se/N/π inter-actions are observed.

[4-(Dimethyl-amino)-phen-yl]diphenyl-phosphine selenide.

In the title compound, C(20)H(20)NPSe, the P atom lies in a distorted tetra-hedral environment. The Tolman cone angle is 157° indicating steric crowding at this atom. In the crystal, weak C-H⋯Se inter-actions create linked dimeric units and C-H⋯π inter-actions are also observed.

cis-Bis(benzyl-diphenyl-phosphane-κP)dichloridoplatinum(II) dichloro-methane sesquisolvate.

The asymmetric unit of the title compound, [PtCl(2)(C(19)H(17)P)(2)](2)·3CH(2)Cl(2), contains two complex mol-ecules and three dichloro-methane solvent mol-ecules, two of which are disordered over various positions. The Pt(II) complexes reveal a slightly distorted square-planar geometry with average Pt-P and Pt-Cl bond lengthss of 2.252 (8) and 2.363 (8) Å, respectively, and average P-Pt-P and Cl-Pt-Cl angles of 99.17 (8) and 87.1 (7)°, respectively.

(Acetyl-acetonato-κO,O')carbon-yl{dicyclo-hex-yl[4-(dimethyl-amino)-phen-yl]phosphane-κP}rhodium(I).

The title compound, [Rh(C(5)H(7)O(2))(C(20)H(32)NP)(CO)], features an acetyl-acetonate-chelated Rh(I) cation coordinated by one P [Rh-P = 2.2525 (7) Å], one carbonyl C [Rh-C = 1.792 (3) Å] and two O [Rh-O = 2.0582 (17) and 2.0912 (18) Å] atoms in a slightly distorted square-planar geometry. Mol-ecules are packed in positions of least steric hindrance, with the phosphane ligands positioned above and below the Rh-acetyl-acetonate backbone.