The impact of hydrogen bonding on 100% photo-switching in solid-state nitro-nitrito linkage isomers

Two crystal systems: [Pd(Et4dien)(NO2)]OTf [1] and [Pt(Et4dien)(NO2)]OTf [2] (Et4dien = N,N,N′,N′-tetraethyldiethylene-triamine, OTf = trifluoromethanesulfonate) are investigated by steady-state photocrystallographic methods. Both structures contain intermolecular hydrogen bonds to the ground state nitro-(η1-NO2) isomer, which are previously shown to limit the achievable level of nitro → nitrito photo-conversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process

Differences in client and therapist views of the working alliance in drug treatment

Background - There is growing evidence that the therapeutic alliance is one of the most consistent predictors of retention and outcomes in drug treatment. Recent psychotherapy research has indicated that there is a lack of agreement between client, therapist and observer ratings of the therapeutic alliance; however, the clinical implications of this lack of consensus have not been explored. Aims - The aims of the study are to (1) explore the extent to which, in drug treatment, clients and counsellors agree in their perceptions of their alliance, and (2) investigate whether the degree of disagreement between clients and counsellors is related to retention in treatment. Methods - The study recruited 187 clients starting residential rehabilitation treatment for drug misuse in three UK services. Client and counsellor ratings of the therapeutic alliance (using the WAI-S) were obtained during weeks 1-12. Retention was in this study defined as remaining in treatment for at least 12 weeks. Results - Client and counsellor ratings of the alliance were only weakly related (correlations ranging from r = 0.07 to 0.42) and tended to become more dissimilar over the first 12 weeks in treatment. However, whether or not clients and counsellors agreed on the quality of their relationship did not influence whether clients were retained in treatment. Conclusions - The low consensus between client and counsellor views of the alliance found in this and other studies highlights the need for drug counsellors to attend closely to their clients' perceptions of the alliance and to seek regular feedback from clients regarding their feelings about their therapeutic relationship

Inverse monoids and immersions of 2-complexes

It is well known that under mild conditions on a connected topological space $\mathcal X$, connected covers of $\mathcal X$ may be classified via conjugacy classes of subgroups of the fundamental group of $\mathcal X$. In this paper, we extend these results to the study of immersions into 2-dimensional CW-complexes. An immersion $f : {\mathcal D} \rightarrow \mathcal C$ between CW-complexes is a cellular map such that each point $y \in {\mathcal D}$ has a neighborhood $U$ that is mapped homeomorphically onto $f(U)$ by $f$. In order to classify immersions into a 2-dimensional CW-complex $\mathcal C$, we need to replace the fundamental group of $\mathcal C$ by an appropriate inverse monoid. We show how conjugacy classes of the closed inverse submonoids of this inverse monoid may be used to classify connected immersions into the complex

Technical Note: Molecular characterization of aerosol-derived water soluble organic carbon using ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Despite the acknowledged relevance of aerosol-derived water-soluble organic carbon (WSOC) to climate and biogeochemical cycling, characterization of aerosol WSOC has been limited. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was utilized in this study to provide detailed molecular level characterization of the high molecular weight (HMW; m/z>223) component of aerosol-derived WSOC collected from rural sites in Virginia and New York, USA. More than 3000 peaks were detected by ESI FT-ICR MS within a m/z range of 223–600 for each sample. Approximately 86% (Virginia) and 78% (New York) of these peaks were assigned molecular formulas using only carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and sulfur (S) as elemental constituents. H/C and O/C molar ratios were plotted on van Krevelen diagrams and indicated a strong contribution of lignin-like and lipid-like compounds to the aerosol-derived WSOC samples. Approximately 1–4% of the peaks in the aerosol-derived WSOC mass spectra were classified as black carbon (BC) on the basis of double bond equivalents calculated from the assigned molecular formulas. In addition, several high-magnitude peaks in the mass spectra of samples from both sites corresponded to molecular formulas proposed in previous secondary organic aerosol (SOA) laboratory investigations indicating that SOAs are important constituents of the WSOC. Overall, ESI FT-ICR MS provides a level of resolution adequate for detailed compositional and source information of the HMW constituents of aerosol-derived WSOC

Solid-state photochemistry of molecular photo-switchable species:the role of photocrystallographic techniques

Over the last 30 years, the single-crystal photocrystallographic technique has been developed to determine the three-dimensional crystal and mol­ecular structures of metastable species which have been generated in the crystal photochemically. Transition-metal complexes that have been investigated using this methodology include complexes that contain nitrosyl, di­nitro­gen, sulfur dioxide and nitrite ligands, all of which form new linkage isomers in the solid state when photoactivated by light of the appropriate wavelength. Both steric and electronic factors determine the level of the conversion from the ground-state structure to the metastable isomeric structure, and both the `reaction cavity' size and the nature of the inter­molecular inter­actions are shown to be among the key factors that influence the percentage conversion

Homotopy types of stabilizers and orbits of Morse functions on surfaces

Let $M$ be a smooth compact surface, orientable or not, with boundary or without it, $P$ either the real line $R^1$ or the circle $S^1$, and $Diff(M)$ the group of diffeomorphisms of $M$ acting on $C^{\infty}(M,P)$ by the rule $h\cdot f\mapsto f \circ h^{-1}$, where $h\in Diff(M)$ and $f \in C^{\infty}(M,P)$. Let $f:M \to P$ be a Morse function and $O(f)$ be the orbit of $f$ under this action. We prove that $\pi_k O(f)=\pi_k M$ for $k\geq 3$, and $\pi_2 O(f)=0$ except for few cases. In particular, $O(f)$ is aspherical, provided so is $M$. Moreover, $\pi_1 O(f)$ is an extension of a finitely generated free abelian group with a (finite) subgroup of the group of automorphisms of the Reeb graph of $f$. We also give a complete proof of the fact that the orbit $O(f)$ is tame Frechet submanifold of $C^{\infty}(M,P)$ of finite codimension, and that the projection $Diff(M) \to O(f)$ is a principal locally trivial $S(f)$-fibration.Comment: 49 pages, 8 figures. This version includes the proof of the fact that the orbits of a finite codimension of tame action of tame Lie group on tame Frechet manifold is a tame Frechet manifold itsel

Earth‐Moon‐Mars Radiation Environment Module framework

[1] We are preparing to return humans to the Moon and setting the stage for exploration to Mars and beyond. However, it is unclear if long missions outside of low-Earth orbit can be accomplished with acceptable risk. The central objective of a new modeling project, the Earth-Moon-Mars Radiation Exposure Module (EMMREM), is to develop and validate a numerical module for characterizing time-dependent radiation exposure in the Earth-Moon-Mars and interplanetary space environments. EMMREM is being designed for broad use by researchers to predict radiation exposure by integrating over almost any incident particle distribution from interplanetary space. We detail here the overall structure of the EMMREM module and study the dose histories of the 2003 Halloween storm event and a June 2004 event. We show both the event histories measured at 1 AU and the evolution of these events at observer locations beyond 1 AU. The results are compared to observations at Ulysses. The model allows us to predict how the radiation environment evolves with radial distance from the Sun. The model comparison also suggests areas in which our understanding of the physics of particle propagation and energization needs to be improved to better forecast the radiation environment. Thus, we introduce the suite of EMMREM tools, which will be used to improve risk assessment models so that future human exploration missions can be adequately planned for

An infinite genus mapping class group and stable cohomology

We exhibit a finitely generated group \M whose rational homology is isomorphic to the rational stable homology of the mapping class group. It is defined as a mapping class group associated to a surface \su of infinite genus, and contains all the pure mapping class groups of compact surfaces of genus $g$ with $n$ boundary components, for any $g\geq 0$ and $n>0$. We construct a representation of \M into the restricted symplectic group ${\rm Sp_{res}}({\cal H}_r)$ of the real Hilbert space generated by the homology classes of non-separating circles on \su, which generalizes the classical symplectic representation of the mapping class groups. Moreover, we show that the first universal Chern class in H^2(\M,\Z) is the pull-back of the Pressley-Segal class on the restricted linear group ${\rm GL_{res}}({\cal H})$ via the inclusion ${\rm Sp_{res}}({\cal H}_r)\subset {\rm GL_{res}}({\cal H})$.Comment: 14p., 8 figures, to appear in Commun.Math.Phy

Topics on the geometry of D-brane charges and Ramond-Ramond fields

In this paper we discuss some topics on the geometry of type II superstring backgrounds with D-branes, in particular on the geometrical meaning of the D-brane charge, the Ramond-Ramond fields and the Wess-Zumino action. We see that, depending on the behaviour of the D-brane on the four non-compact space-time directions, we need different notions of homology and cohomology to discuss the associated fields and charge: we give a mathematical definition of such notions and show their physical applications. We then discuss the problem of corretly defining Wess-Zumino action using the theory of p-gerbes. Finally, we recall the so-called *-problem and make some brief remarks about it.Comment: 29 pages, no figure

Explicit expressions for the topological defects of spinor Bose-Einstein condensates

In this paper we first derive a general method which enables one to create expressions for vortices and monopoles. By using this method we construct several order-parameters describing the vortices and monopoles of Bose-Einstein condensates with hyperfine spin F=1 and F=2. We concentrate on defects which are topologically stable in the absence of an external magnetic field. In particular we show that in a ferromagnetic condensate there can be a vortex which does not produce any superfluid flow. We also point out that the order-parameter space of the cyclic phase of F=2 condensate consists of two disconnected sets. Finally we examine the effect of an external magnetic field on the vortices of a ferromagnetic F=1 condensate and discuss the experimental preparation of a vortex in this system.Comment: 17 pages, partly rewritten to improve clarity, conclusions unchange