Elevated serum cytokine levels in mesothelioma patients who have undergone pleurectomy or extrapleural pneumonectomy and adjuvant intraoperative photodynamic therapy

Patients treated on a Phase-I clinical trial of photodynamic therapy (PDT) developed a systemic capillary leak syndrome that constituted the dose-limiting toxicity. We examined serum samples from patients treated at the maximally tolerated dose level for evidence of a systemic, cytokine-mediated inflammatory response. Patients underwent pleurectomy or extrapleural pneumonectomy (EPP) followed by intraoperative PDT of the thorax using Foscan at a dose of 0.1 mg/kg 6 days before surgery and 652 nm red light at a dose of 10 J/cm2. Levels of interferon-gamma (IFN-gamma), tumor necrosis factor-alpha (TNF-alpha), interleukin (IL)-1beta, IL-6, IL-8, IL-10 and IL-12 were assayed before Foscan administration; after anesthetic induction, surgical resection and light delivery; in postoperative recovery and the day after the surgery. Of the analyzed patients, eight underwent a pleurectomy and one an EPP followed by PDT. IFN-gamma, TNF-alpha and IL-12 showed no elevation, but IL-1beta, IL-6, IL-8 and IL-10 levels were elevated after surgery and PDT. IL-1beta showed a statistically significant variation from baseline after surgery and IL-6, after PDT. The results suggest a systemically mediated inflammatory response resulting from thoracic surgery followed by PDT. Further investigation of specific mechanisms is warranted.     

Three-coordinate organoboron compounds BAr2R (Ar = mesityl, R = 7-azaindolyl- or 2,2'-dipyridylamino-functionalized aryl or thienyl) for electroluminescent devices and supramolecular assembly

Eight novel three-coordinate boron compounds with the general formula BAr(2)L, in which Ar is mesityl and L is a 7-azaindolyl- or a 2,2'-dipyridylamino-functionalized aryl or thienyl ligand, have been synthesized by Suzuki coupling, Ullmann condensation methods, or simple substitution reactions (L = p-(2,2'-dipyridylamino)phenyl, 1; p-(2,2'-dipyridylamino)biphenyl, 2; p-(7-azaindolyl)phenyl, 3; p-(7-azaindolyl)biphenyl, 4; 3,5-bis(2,2'-dipyridylamino)phenyl, 5; 3,5-bis(7-azaindolyl)phenyl, 6; p-[3,5-bis(2,2'-dipyridylamino)phenyl]phenyl, 7; 5-[p-(2,2'-dipyridylamino)phenyl]-2-thienyl, 8). The structures of 1, 3, and 5-7 have been determined by X-ray diffraction analyses. These new boron compounds are bright blue emitters. Electroluminescent devices using compound 2 or 8 as the emitter and the electron-transport layer have been successfully fabricated. Molecular orbital calculations (Gaussian 98) have established that the blue emission of compounds 1-8 originates from charge transfer between the pi orbital of the ligand L and the p(pi) orbital of the boron center. The ability of these boron compounds to bind to metal centers to form supramolecular assemblies was demonstrated by treatment of compound 2 with Zn(O(2)CCF(3))(2), which generated a 1:1 chelate complex [2.Zn(O(2)CCF(3))(2)] (10), and also by treatment of compound 4 with AgNO(3), yielding a 2:1 coordination compound [(4)(2).Ag(NO(3))] (11). In the solid state, compounds 10 and 11 form interesting head-to-head and tail-to-tail extended structures that host solvent molecules such as benzene.     

Effect of the Ar-Ni(s) potential on the cross section for Ar+CH4/Ni{111} collision-induced desorption and the need for a more accurate CH4/Ni{111} potential

In a previous paper [L. Sun, P. de Sainte Claire, O. Meroueh, and W. L Hase, J. Chem. Phys. 114, 535 (2001)], a classical trajectory simulation was reported of CH(4) desorption from Ni{111} by Ar-atom collisions. At an incident angle theta(i) of 60 degrees (with respect to the surface normal), the calculated collision-induced desorption (CID) cross sections are in excellent agreement with experiment. However, for smaller incident angles the calculated cross sections are larger than the experimental values and for normal collisions, theta(i)=0 degrees , the calculated cross sections are approximately a factor of 2 larger. This trajectory study used an analytic function for the Ar+Ni(s) intermolecular potential which gives an Ar-Ni{111} potential energy minimum which is an order of magnitude too deep. In the work reported here, the previous trajectory study is repeated with an Ar+Ni(s) analytic intermolecular potential which gives an accurate Ar-Ni{111} potential energy minimum and also has a different surface corrugation than the previous potential. Though there are significant differences between the two Ar+Ni(s) analytic potentials, they have no important effects on the CID dynamics and the cross sections reported here are nearly identical to the previous values. Zero-point energy motions of the surface and the CH(4)-Ni(s) intermolecular modes are considered in the simulation and they are found to have a negligible effect on the CID cross sections. Calculations of the intermolecular potential between CH(4) and a Ni atom, at various levels of theory, suggest that there are substantial approximations in the ab initio calculation used to develop the CH(4)+Ni{111} potential. The implication is that the differences between the trajectory and experimental CID cross sections may arise from an inaccurate CH(4)+Ni{111} potential used in the trajectory simulation.     

K2NdP2S7: A Mixed‐Valent Neodymium(III) Thiophosphate According to K4Nd2[PS4]2[P2S6] with Discrete [PS4]3– and [S3P–PS3]4– Anions

Pale blue, lath‐shaped single crystals of K₂NdP₂S₇ (≡ K₄Nd₂[PS₄]₂[P₂S₆]; monoclinic, P2₁/n, a = 904.76(8), b = 677.38(6), c = 1988.7(2) pm, β = 97.295(5)°, Z = 2) are obtained by the reaction of Nd, S and P₂S₅ with an excess of KCl as a flux in evacuated silica tubes at 750 °C (7 d) which should produce Nd[PS₄] instead. Beside isolated [PS₄]^3– tetrahedra, the crystal structure contains discrete ethane‐analogous [P₂S₆]^4– (≡ [S₃P–PS₃]^4–) units in staggered conformation with tetravalent phosphorus cations and a P–P distance of 219 pm. The two crystallographically different potassium cations show coordination numbers of nine and ten in the shape of distorted mono‐ and bicapped square antiprisms. Finally, the Nd³⁺ cations are surrounded by eight sulfur atoms arranged as (uncapped) square antiprisms. The entire structure is dominated by (K1)⁺ containing {(Nd₂[PS₄]₂[P₂S₆])^4–} layers parallel (101) which are three‐dimensionally interconnected by (K2)⁺ cations.     

Vanadin-Bestimmungsmethoden

Ohne Zusammenfassung     

Debenzylation using catalytic hydrogenolysis in trifluoroethanol, and the total synthesis of (−)-raumacline

N-Debenzylations using catalytic hydrogenolysis often fail to take place unless alcoholic solvents are used, but this can lead to N-alkylation as a side reaction; using trifluoroethanol as the solvent overcomes this problem, and leads to highly reliable hydrogenolyses for a wide range of substrates, including the final deprotection step in our total synthesis of (−)-raumacline.     

Yuri Alexeev,Theresa L. Windus,Chang‐Guo Zhan,David A. Dixon,Erratum to “Accurate heats of formation and acidities for H3PO4, H2SO4, and H2CO3 from ab initio electronic structure calculations,” International Journal of Quantum Chemistry (2005) 102(5) 775–784

The original article to which this Erratum refers was published in International Journal of Quantum Chemistry (2005) 102(5) 775–784     

Enumeration of pairs of permutations

Let π = (a₁, a₂, …, a_n), ? = (b₁, b₂, …, b_n) be two permutations of $\text{Z}{}_{\mathrm{n}}\text{= {1, 2, …, n}}$. A rise of π is pair a_i, a_i+1 with a_i < a_i+1; a fall is a pair a_i, a_i+1 with a_i > a_i+1. Thus, for i = 1, 2, …, n ? 1, the two pairs a_i, a_i+1; b_i, b_i+1 are either both rises, both falls, the first a rise and the second a fall or the first a fall and the second a rise. These possibilities are denoted by RR, FF, RF, FR. The paper is concerned with the enumeration of pairs π, p with a given number of RR, FF, RF, FR. In particular if ω_n denotes the number of pairs with RR forbidden, it is proved that $\text{∑}{}^{\mathrm{\infty }}{}_0\text{ω}{}_{\mathrm{n}}\text{z}{}^{\mathrm{n}}\text{n!n!}\text{=}\text{1}\text{?(z)}$, $\text{?(z) = ∑}{}^{\mathrm{\infty }}{}_0\text{(-1)}{}^{\mathrm{n}}\text{z}{}^{\mathrm{n}}\text{n!n!}$. More precisely if ω(n, k) denotes the number of pairs π, p with exactly k occurences of RR(or FF, RF, FR) then $\text{1 + ∑}{}^{\mathrm{\infty }}{}_{\mathrm{n=1}}\text{z}{}^{\mathrm{n}}\text{n!n!}$$\text{∑}{}^{\mathrm{n?1}}{}_{\mathrm{k=0}}\text{ω(n, k)x}{}^{\mathrm{k}}\text{=}\text{(1 ? x)}\text{(?(z(1 ? x)) ? x)}$.     

Zur Kenntnis cyclischer Acylale, 1. Mitt.

Zusammenfassung Bei einem cyclischen Acylal, dem Isopropylidenmalonat (Meldrum-Säure), wurde die Frage der CH-Acidität durch Austauschversuche mit Deuterium und IR-spektroskopische Messungen geklärt. Weiters wurde die Struktur zweier anderer cyclischer Acylale bewiesen, sowie einige eigentümliche Reaktionen dieser Körperklasse aufgefunden und untersucht.Mit 3 Abbildungen