bluuebunny/crossref_metadata_2025 huggingface dataset:
Guiding conservation efforts in the Hantam–Tanqua–Roggeveld (South Africa) using diversity parameters
Authors: Van der Merwe Helga , Van Rooyen Margaretha W.
Published: September 2011

The Hantam–Tanqua–Roggeveld subregion falls within the Succulent Karoo and Fynbos Biomes, which are both recognised as global biodiversity hotspots that should be conserved. The objective of this study was to gather baseline biodiversity information that can be used to guide conservation efforts. A total of 40 Whittaker plots were surveyed in the subregion and the various diversity parameters calculated from the data were compared across the subregion and to available data for the Succulent Karoo and Fynbos Biomes. Species richness per 1000 m2 ranged from nine to 100 species across the subregion. Species richness for all plot sizes < 1000 m2 was significantly lower for the Tanqua Karoo than for both the Winter Rainfall Karoo and Mountain Renosterveld. The latter two areas did not differ significantly from each other with regard to species richness. Species richness was significantly higher only at the 1000 m2 scale in the Mountain Renosterveld compared to the Winter Rainfall Karoo. Evenness and Shannon and Simpson indices did not differ significantly between the Mountain Renosterveld and Winter Rainfall Karoo; however, these values were significantly higher than for the Tanqua Karoo. A principal coordinate analysis of species richness data at seven plot sizes produced three distinct clusters. One cluster represented the Tanqua Karoo, with low species richness, evenness, and Shannon and Simpson indices. Another cluster represented mostly Mountain Renosterveld vegetation, which was characterised by a high species richness, evenness, and Shannon and Simpson indices. The third cluster was formed by the remaining Mountain Renosterveld plots as well as the Winter Rainfall Karoo plots.The high species richness values found in the various vegetation units can add valuable information to the conservation planning arena by providing information on biodiversity parameters and their spatial distribution. This information can assist with conservation efforts in the Hantam, Tanqua and Roggeveld areas.Conservation implications: Conservation and development of the Hantam–Tanqua– Roggeveld subregion is hampered by a lack of information on floristic diversity. The results of the current study indicated areas of low diversity and contrasting areas of high diversity. These data can be used to guide effective conservation and management of the floristic diversity.
Exposure Assessment of Mercury and Its Compounds by Dispersion Modeling: A Case Study in the Sea of Japan Coastal Area
Authors: Razi Khandakar Habib Al , Hiroshi Moritomi , Shinji Kambara
Published: September 2011

In Japan, mercury and its compounds were categorized as hazardous air pollutants in 1996 and are on the list of “Substances Requiring Priority Action” published by the Central Environmental Council of Japan. The Air Quality Management Division of the Environmental Bureau, Ministry of the Environment, Japan, selected the current annual mean environmental air quality standard for mercury and its compounds of 0.04 μg/m3. Long-term exposure to mercury and its compounds can have a carcinogenic effect, inducing eg, Minamata disease. This study evaluates the impact of mercury emissions on air quality in the coastal area of the Sea of Japan. Average yearly emission of mercury from an elevated point source in this area with background concentration and one-year meteorological data were used to predict the ground level concentration of mercury. The annual mean concentration distribution of mercury and its compounds were calculated for the middle part of Honshu Island, which served as a background level of mercury concentration for the coastal are of the Sea of Japan. To estimate the concentration of mercury and its compounds in air of the local area, two different simulation models have been used. The first is the National Institute of Advanced Science and Technology Atmospheric Dispersion Model for Exposure and Risk Assessment (AIST-ADMER) that estimates regional atmospheric concentration and distribution. The second is the Ministry of Economy, Trade and Industry Low Rise Industrial Source Dispersion Model (METI-LIS) that estimates the atmospheric concentration distribution in the vicinity of facilities.
Safety and Efficacy of Vigabatrin for the Treatment of Infantile Spasms
Authors: Faulkner Michele A. , Tolman Justin A.
Published: September 2011

In 2009, vigabatrin became the first FDA approved medication for the treatment of infantile spasms in the United States. There are few well-designed prospective studies comparing the drug to placebo or other modalities used in the treatment of infantile spasms. The available data have demonstrated that vigabatrin is efficacious in the treatment of infantile spasms regardless of underlying etiology, but that it is particularly beneficial in patients with a diagnosis of tuberous sclerosis. Adrenocorticotropic hormone (ACTH), the only other medication with robust efficacy data, has been used as first line therapy for infantile spasms associated with other etiologies, and in general controls spasms sooner than vigabatrin, though relapse is common with both therapies. Vigabatrin is generally well tolerated. However, use has been associated with permanent loss of peripheral vision in some patients. In children with tuberous sclerosis, vigabatrin should be considered as initial therapy for infantile spasms. It is a viable alternative for patients with suboptimal response, contraindications or intolerance to ACTH.
Awareness and uptake of recommended vaccines among immunosuppressed patients
Authors: Savage J , Muller F , Ormerod AD
Published: September 2011

The Green Book recommended in 2009 that immunosuppressed patients should be receiving the yearly seasonal flu vaccine, the pandemic swine influenza A H1N1/09 vaccine and should have had the single pneumococcal vaccination. A retrospective audit in 2010 involving 60 immunosuppressed patients revealed that 83.3% of participants were aware of their entitlement to the vaccines. The majority were informed by their GP practice rather than the prescribing specialist. In 2009, 70% of participants received the seasonal flu vaccine, 40% received the H1N1 vaccine and 21.6% had received the pneumococcal vaccine. Reasons given for not receiving the recommended vaccines were lack of awareness, reported by 37.5%, followed by worries regarding side-effects reported by 25%. The data suggest that uptake rates, particularly for pneumococcal vaccination, could be improved with targeted information and promotion at the point of commencing immunosuppressants and approaching the influenza season. Prescribing physicians should take a more active role in routinely promoting and planning vaccination for at-risk groups and should provide information on how to receive the recommended vaccines and their side-effect profiles.
Anaemia is of prognostic significance in patients with oesophageal adenocarcinoma
Authors: Tanswell I , Steed H , Butterworth J , Townson G
Published: September 2011

Anaemia is common in a wide range of malignancies and individual studies have demonstrated it to be an independent prognostic marker for survival in certain cancer types. The study population consisted of 171 patients: 77 anaemic and 94 non-anaemic. Sixty per cent of the study population had adenocarcinoma with 37% having squamous cell carcinoma. Late-stage disease occurred in 80% of individuals. There was no significant difference in survival times between the two groups (p=0.1), and after adjusting for confounding factors including age, sex, stage and physical status (p=0.8). Anaemic individuals with adenocarcinoma suffered a poorer survival probability compared to those with normal haemoglobon level (p=0.02). Anaemia is common at diagnosis in oesophageal cancer and was found to be a significant prognostic indicator of survival in adenocarcinoma, but not squamous cell carcinoma.
A case study of aerosol processing and evolution in summer in New York City
Authors: Sun Y. L. , Zhang Q. , Schwab J. J. , Chen W. N. , Bae M. S. , Lin Y. C. , Hung H. M. , Demerjian K. L.
Published: September 2011

Abstract. We have investigated an aerosol processing and evolution event from 21–22 July during the summer 2009 Field Intensive Study at Queens College in New York City (NYC). The evolution processes are characterized by three consecutive stages: (1) aerosol wet scavenging, (2) nighttime nitrate formation, and (3) photochemical production and evolution of secondary aerosol species. Our results suggest that wet scavenging of aerosol species tends to be strongly related to their hygroscopicities and also mixing states. The scavenging leads to a significant change in bulk aerosol composition and average carbon oxidation state because of scavenging efficiencies in the following order: sulfate > low-volatility oxygenated organic aerosol (LV-OOA) > semi-volatile OOA (SV-OOA) > hydrocarbon-like OA (HOA). The second stage involves a quick formation of nitrate from heterogeneous reactions at nighttime. During the third stage, simultaneous increases of sulfate and SV-OOA were observed shortly after sunrise, indicating secondary aerosol formation. Organic aerosol particles become highly oxidized in ~half day as the result of photochemical processing, consistent with previously reported results from the CO-tracer method (OA/ΔCO). The photochemical reactions appear to progress gradually associated with a transformation of semi-volatile OOA to low-volatility species based on the evolution trends of oxygen-to-carbon (O/C) ratio, relationship between f44 (fraction of m/z 44 in OA) and f43 (fraction of m/z 43 in OA), and size evolution of OOA and HOA. Aerosols appear to become more internally mixed during the processing. Our results suggest that functionalization by incorporation of both C and O plays a major role in the early period of OA oxidation (O/C <0.5). Our results also show that photochemical production of LV-OOA during this event is approximately a few hours behind of sulfate production, which might explain the sometimes lack of correlations between LV-OOA and sulfate, two secondary aerosol species which often exist in internal mixtures over regional scales.
Meteorological observations of the coastal boundary layer structure at the Bulgarian Black Sea coast
Authors: Barantiev D. , Novitsky M. , Batchvarova E.
Published: September 2011

Abstract. Continuous wind profile and turbulence measurements were initiated in July 2008 at the coastal meteorological observatory of Ahtopol on the Black Sea (south-east Bulgaria) under a Bulgarian-Russian collaborative program. These observations are the start of high resolution atmospheric boundary layer vertical structure climatology at the Bulgarian Black Sea coast using remote sensing technology and turbulence measurements. The potential of the measurement program with respect to this goal is illustrated with examples of sea breeze formation and characteristics during the summer of 2008. The analysis revealed three distinct types of weather conditions: no breeze, breeze with sharp frontal passage and gradually developing breeze. During the sea breeze days, the average wind speed near the ground (from sonic anemometer at 4.5 m and first layer of sodar at 30–40 m) did not exceed 3–4 m s−1. The onset of breeze circulation was detected based on surface layer measurements of air temperature (platinum sensor and acoustic), wind speed and direction, and turbulence parameters. The sodar measurements revealed the vertical structure of the wind field.
Large-scale groundwater modeling using global datasets: a test case for the Rhine-Meuse basin
Authors: Sutanudjaja E. H. , van Beek L. P. H. , de Jong S. M. , van Geer F. C. , Bierkens M. F. P.
Published: September 2011

Abstract. The current generation of large-scale hydrological models does not include a groundwater flow component. Large-scale groundwater models, involving aquifers and basins of multiple countries, are still rare mainly due to a lack of hydro-geological data which are usually only available in developed countries. In this study, we propose a novel approach to construct large-scale groundwater models by using global datasets that are readily available. As the test-bed, we use the combined Rhine-Meuse basin that contains groundwater head data used to verify the model output. We start by building a distributed land surface model (30 arc-second resolution) to estimate groundwater recharge and river discharge. Subsequently, a MODFLOW transient groundwater model is built and forced by the recharge and surface water levels calculated by the land surface model. Results are promising despite the fact that we still use an offline procedure to couple the land surface and MODFLOW groundwater models (i.e. the simulations of both models are separately performed). The simulated river discharges compare well to the observations. Moreover, based on our sensitivity analysis, in which we run several groundwater model scenarios with various hydro-geological parameter settings, we observe that the model can reasonably well reproduce the observed groundwater head time series. However, we note that there are still some limitations in the current approach, specifically because the offline-coupling technique simplifies the dynamic feedbacks between surface water levels and groundwater heads, and between soil moisture states and groundwater heads. Also the current sensitivity analysis ignores the uncertainty of the land surface model output. Despite these limitations, we argue that the results of the current model show a promise for large-scale groundwater modeling practices, including for data-poor environments and at the global scale.
On the uncertainties associated with using gridded rainfall data as a proxy for observed
Authors: Tozer C. R. , Kiem A. S. , Verdon-Kidd D. C.
Published: September 2011

Abstract. Gridded rainfall datasets are used in many hydrological and climatological studies, in Australia and elsewhere, including for hydroclimatic forecasting, climate attribution studies and climate model performance assessments. The attraction of the spatial coverage provided by gridded data is clear, particularly in Australia where the spatial and temporal resolution of the rainfall gauge network is sparse. However, the question that must be asked is whether it is suitable to use gridded data as a proxy for observed point data, given that gridded data is inherently "smoothed" and may not necessarily capture the temporal and spatial variability of Australian rainfall which leads to hydroclimatic extremes (i.e. droughts, floods)? This study investigates this question through a statistical analysis of three monthly gridded Australian rainfall datasets – the Bureau of Meteorology (BOM) dataset, the Australian Water Availability Project (AWAP) and the SILO dataset. To demonstrate the hydrological implications of using gridded data as a proxy for gauged data, a rainfall-runoff model is applied to one catchment in South Australia (SA) initially using gridded data as the source of rainfall input and then gauged rainfall data. The results indicate a markedly different runoff response associated with each of the different sources of rainfall data. It should be noted that this study does not seek to identify which gridded dataset is the "best" for Australia, as each gridded data source has its pros and cons, as does gauged or point data. Rather the intention is to quantify differences between various gridded data sources and how they compare with gauged data so that these differences can be considered and accounted for in studies that utilise these gridded datasets. Ultimately, if key decisions are going to be based on the outputs of models that use gridded data, an estimate (or at least an understanding) of the uncertainties relating to the assumptions made in the development of gridded data and how that gridded data compares with reality should be made.
Brief communication "Climatic covariates for the frequency analysis of heavy rainfall in the Mediterranean region"
Authors: Tramblay Y. , Neppel L. , Carreau J.
Published: September 2011

Abstract. In Mediterranean regions, climate studies indicate for the future a possible increase in the extreme rainfall events occurrence and intensity. To evaluate the future changes in the extreme event distribution, there is a need to provide non-stationary models taking into account the non-stationarity of climate. In this study, several climatic covariates are tested in a non-stationary peaks-over-threshold modeling approach for heavy rainfall events in Southern France. Results indicate that the introduction of climatic covariates could improve the statistical modeling of extreme events. In the case study, the frequency of southern synoptic circulation patterns is found to improve the occurrence process of extreme events modeled via a Poisson distribution, whereas for the magnitude of the events, the air temperature and sea level pressure appear as valid covariates for the Generalized Pareto distribution scale parameter. Covariates describing the humidity fluxes at monthly and seasonal time scales also provide significant model improvements for the occurrence and the magnitude of heavy rainfall events. With such models including climatic covariates, it becomes possible to asses the risk of extreme events given certain climatic conditions at monthly or seasonal timescales. The future changes in the heavy rainfall distribution can also be evaluated using covariates computed by climate models.
A New Galactic Wolf-Rayet Star in Centaurus
Authors: Roman-Lopes A.
Published: September 2011

I communicate the detection of a new Galactic Wolf-Rayet star (WR60a) in Centaurus. The H- and
K-band spectra of WR60a show strong carbon near-infrared emission lines, characteristic of Wolf-Rayet stars of the
WC5-7 subtype. Adopting mean absolute magnitude MK and mean intrinsic (J-KS) and (H-KS) colours, it was found that WR60a suffers a mean visual extinction of 3.8±1.3 magnitudes, being located at a probable heliocentric
distance of 5.2±0.8 Kpc, which for the related Galactic longitude (l=312) puts this star probably in the Carina-Sagittarius arm at about 5.9 kpc from the Galactic center. I searched for clusters in the vicinity of WR60a
and in principle found no previously known clusters in a search radius region of several tens arcminutes. The detection of a
well-isolated WR star induced us to seek for some still unknown cluster, somewhere in the vicinity of WR60a. From
inspection of 5.8 μm and 8.0 μm Spitzer/IRAC GLIMPSE images of the region around the new WR star,
strong mid-infrared extended emission at about 13.5 arcmin south-west of WR60a was found.
The study of the H-KS colour
distribution of point sources associated with the extended emission reveals the presence of a new Galactic cluster
candidate probably formed by at least 85 stars.
On Hyperideals in Left Almost Semihypergroups
Authors: Hila Kostaq , Dine Jani
Published: September 2011

This paper deals with a class of algebraic hyperstructures called left almost semihypergroups (LA-semihypergroups), which are a generalization of LA-semigroups and semihypergroups. We introduce the notion of LA-semihypergroup, the related notions of hyperideal, bi-hyperideal, and some properties of them are investigated. It is a useful nonassociative algebraic hyperstructure, midway between a hypergroupoid and a commutative hypersemigroup, with wide applications in the theory of flocks, and so forth. We define the topological space and study the topological structure of LA-semihypergroups
using hyperideal theory. The topological spaces formation guarantee for the preservation of finite intersection and arbitrary union between the set of hyperideals and the open subsets of resultant topologies.
Liquid Chromatography‐Mass Spectrometry in Analytical Clinical Chemistry
Authors: Sluss, PhD Patrick M.
Published: September 2011

This article is intended to provide a basic understanding of the principles and current configurations of liquid chromatography tandem mass spectrometry (LC/MS/MS) technologies used in clinical laboratories. Multidimensional liquid chromatography (LC), interfacing with mass spectrometry (MS) using soft ionization systems, and the principles of modern mass spectrometers, quadrupole, time‐of‐flight (TOF), and Fourier transform ion cyclotron resonance, are discussed. The principles of ion traps and orbitraps are discussed as these technologies are increasingly being applied in clinical laboratories. As LC/MS/MS applications in the clinical laboratory continue to grow at an unprecedented rate, it is critical for clinical pathologists and laboratorians to understand the principles, design, and limitations of the technologies involved.
Microwave‐Assisted Sample Preparation for Spectrochemistry
Authors: Nóbrega Joaquim A. , Donati George L.
Published: September 2011

Microwave‐assisted sample preparation was a major developmental step in combining the overall quality and speediness of spectrochemical analysis with the initial step of converting solid samples into representative solutions. Instrumentation and applications for organic and inorganic samples are discussed in detail after briefly addressing the fundamentals of the method. The feasibility of using diluted acid solutions and pressurized oxygen vessels for sample digestion is rationalized and clearly related to recent advances in reaction vessel materials and the interaction between matter and microwave radiation. Applications based on microwave‐induced combustion (MIC) and procedures developed for chemical speciation are also highlighted. A list of ideal attributes for microwave‐assisted sample preparation is proposed and evaluated considering the state of the art. Major needs, mainly related to the capacity of digesting large sample masses and improvements in sample throughput, are also pointed out.
Structure and Dynamics of Carbohydrate Residues. Fluorescence Spectroscopy Studies
Authors: Albani Jihad R.
Published: September 2011

Structure of carbohydrate residues are in general studied via NMR. In the present study, we are describing structural and dynamical studies of carbohydrates bound to α1‐acid glycoprotein using fluorescence spectroscopy as a tool. Also, we applied fluorescence spectroscopy to show importance of a specific fucose in the interaction and stability of two proteins.
Earprint Comparison: Admissibility of Evidence in Court
Authors: Moenssens Andre
Published: September 2011

The admissibility of the conclusion an examiner reached comparing anatomical features observed in a crime scene latent earprint of unknown provenance with corresponding features that may exist in the known image of a suspect's ears has long been a contentious issue in courts that operate in an adversarial system of justice based on Common Law. This article explores the two major appellate‐level decisions on that issue, both of which concluded that the earprint comparison evidence offered in the cases should not have been admitted as evidence. Some further analysis of legal principles that may come into play in such cases is also presented.
Firearms: History
Authors: Heard Brian J.
Published: September 2011

A concise history of firearms from the hand cannon to the modern day centre fire weapon. Includes sections on the rifling rate necessary to stabilise a bullet.
Firearms: Ammunition – History
Authors: Heard Brian J.
Published: September 2011

This article provides a history of ammunition including a list of introduction dates for a large number of cartridges.
Eyewitness Memory Issues in Civil Litigation
Authors: Weaver Charles A. , Krug Kevin S. , Trent Terrell J. , Holmes Amanda E. , Parra Karenna F.
Published: September 2011

The reconstructive nature of memory affects all long‐term recollection—all of us have misremembered events from our past, confused events from different time frames, or failed to remember the names of colleagues. Memory errors in the courtroom are significantly more serious. Mistaken identification can send an innocent person to prison, and those in the legal community acknowledge the valuable contribution of memory researchers in minimizing these errors. But memory plays an equally large role in many areas of civil litigation. Focusing particularly on product liability cases, this article addresses memory in civil litigation. Memory experts do not have any special ability to distinguish true from false memories, in the absence of corroboration. Their expertise, however, encompasses a scientific understanding of factors that are likely to affect the reliability of memories beyond common knowledge and of material assistance to the trier of fact.
Relativistic Electronic Structure Theory for Molecular Spectroscopy
Authors: Mastalerz Remigius , Reiher Markus
Published: September 2011

This review provides a concise introduction to relativistic electronic structure theory with a focus on the prediction of parameters relevant for molecular spectroscopy. For this purpose, a brief overview of wave‐function‐based electronic structure methods with a special focus on the calculation of electron correlation effects is given. These are essential for an accurate prediction of spectroscopic parameters from first‐principles calculations. Then approximate relativistic Hamiltonians are discussed in detail regarding their accuracy and range of application. Thea posterioricalculation of spin–orbit effects from correlated wave functions is briefly described and reviewed. The presentation concludes with an extensive discussion of calculated results for prototypical molecules. The focus is mainly on small molecules to which highly accurate relativistic methods can be applied and close agreement with experimental data can be achieved.
Global Analytical Potential Energy Surfaces for High‐resolution Molecular Spectroscopy and Reaction Dynamics
Authors: Marquardt Roberto , Quack Martin
Published: September 2011

Analytical representations of potential energy hypersurfaces for the nuclear motion in polyatomic molecules from ab initio theory and experiment are discussed in a general way. The qualification of potential hypersurface representations from ab initio theory regarding the description of experimental data from rovibrational high‐resolution spectroscopy and chemical reaction kinetics is analyzed in more detail for a restricted group of molecules including methane, CH4, ammonia, NH3, H2O2, and (HF)2. Current methods for the derivation of analytical representations of potential energy surfaces as well as some applications are reviewed.
AbInitio Calculations for Rydberg States
Authors: Jungen Martin
Published: September 2011

This article deals with the phenomenon of atomic and molecular (electronic) Rydberg series and their quantum chemical treatment on various levels of sophistication, going from the simplefrozen‐corecalculations to the use of highly correlated wave functions.
Indeterminacies of Fitting Parameters in Molecular Spectroscopy
Authors: Watson James K.G.
Published: September 2011

Analyses of molecular spectra often use the idea of aneffective Hamiltonian, in which the dynamical variables are the degrees of freedom involved in the spectrum, and the effects of the other degrees of freedom are represented by the values of various parameters. However, it may not be possible to determine all these parameters by empirical fits of the spectra because different parameters may make indistinguishable contributions to the eigenvalues of the Hamiltonian. This article reviews a number of examples of such indeterminacies, including applications to vibration–rotation spectra of diatomic molecules, without or with corrections for the breakdown of the Born–Oppenheimer approximations; electron‐spin structure in diatomic molecules; centrifugal distortion in asymmetric‐top molecules; vibration–rotation resonances in polyatomic molecules; vibration–rotation interactions in degenerate vibrational states; and internal rotation. The discussion of these indeterminacies involves unitary transformations that are expanded as infinite series. This procedure may break down if the convergence of the series is slow. The study of near‐singularities of least‐squares matrices associated with the presence of indeterminacies is also discussed.
Using Iterative Methods to Compute Vibrational Spectra
Authors: Carrington Tucker
Published: September 2011

In this article, some modern methods for computing vibrational energies of polyatomic molecules are reviewed. The emphasis is on iterative methods with which a spectrum is obtained by evaluating matrix–vector products. To use such methods one does not need to compute or store Hamiltonian matrix elements. If each basis function is a product of functions of a single coordinate, matrix–vector products can be computed by doing sequentailly sums associated with indices of the individual coordinates. The corresponding algorithm is simple and useful, but, with current computers, it cannot be applied to compute the spectrum of a six‐atom molecule. For molecules with six or more atoms (and often for molecules with five atoms), it is necessary to use basis set contraction. A contraction method is presented that has been used for methane and CH5+.
Fourier Transform Microwave Spectroscopy of Doped Helium Clusters
Authors: Jäger Wolfgang , Xu Yunjie
Published: September 2011

In this article, we describe investigations of rotational spectra of complexes and clusters containing helium atoms. These systems are of much interest mainly because of their very low binding energies and the associated relatively large zero‐point energies. As a result, these very weakly bonded systems undergo large amplitude internal stretching and bending motions and the semirigid rotor Hamiltonian can often not describe the spectra appropriately. Microwave spectra of clusters of the type He

N

‐linear molecule are discussed. The number of helium atoms in the cluster,
N
, ranges from 1 up to 39 in the case of He

N

‐carbonyl sulfide. It was possible to record transitions of clusters of successively increasing size and to extract spectroscopic parameters of clusters with atom‐by‐atom resolution. Probably the most significant outcome from these studies is the observation of an increase in the rotational constant,
B
, with increasing
N
. This turnaround occurs at relatively small numbers of helium atoms, e.g.,
N
 = 9 for He

N

‐OCS. The corresponding decrease in moment of inertia with increasing
N
is attributed to a decoupling of helium density from the rotational motion of the dopant molecule. This is interpreted in terms of the occurrence of superfluid effects on the microscopic scale. Throughout the article, we emphasize the importance of our colleagues in infrared spectroscopy and theory collaborating in this research endeavor.
Microwave Spectroscopy of Large Molecules and Molecular Complexes
Authors: Caminati Walther
Published: September 2011

The development of Fourier transform microwave (FTMW) spectroscopy and — most notably — its combination with supersonic‐jet expansion techniques allow for challenging investigations of larger and larger interesting molecular systems.

Large isolated molecules studied by microwave (MW) spectroscopy include long carbon chains of astronomical interest, organic molecules containing two or more aromatic rings, small biomolecules, and transition metal complexes. Often, these systems are characterized by large‐amplitude motions and multifolded conformational and tautomeric equilibria.

Rotational spectra have been reported for many large molecular complexes, such as adducts of large organic and biological molecules with rare gases, water (or other small proton donors/acceptors), and oligomers and hetero adducts of large molecules. Some of these complexes have interaction energies that are in the intermediate regime between bonding and nonbonding (charge‐transfer complexes), and some of them, involving chiral molecules, act as a guide to understanding molecular recognition. In addition, the rotational spectra of several carbonyl sulfide (OCS)Henspecies have been measured (up ton = 39), providing useful data to model superfluidity.

The potentiality of MW spectroscopy to obtain spectroscopic and chemical information on these systems is demonstrated by numerous investigations. Many interesting examples, most of them achieved in the last two decades, have been compiled here.
High‐resolution Microwave and Infrared Spectroscopy of Molecular Cations
Authors: Amano Takayoshi
Published: September 2011

High‐resolution spectroscopic results for molecular cations obtained in the wavelength regions from microwave to infrared are summarized, with emphasis on more recent developments made after the year 2000. Starting at some early stage development made with mostly discharge sources, various experimental techniques developed for the detection of ions are discussed in some details. Recent results on specific molecular ions such as H
3
+
and H
3
O
+
and their isotopic species are reviewed to show what kind of information could be obtained with high‐resolution spectroscopic techniques. The current status on a most challenging species in this field, CH
5
+
, is described. Applications to and implications from astronomical observations are also described wherever they are relevant to spectroscopy.
Rotationally Resolved Electronic Spectroscopy and Automatic Assignment Techniques using Evolutionary Algorithms
Authors: Schmitt Michael , Meerts W. Leo
Published: September 2011

The usefulness of an evolutionary algorithm (EA)‐based approach to the automated evaluation of molecular parameters from various kinds of spectra is shown. The applicability of the method ranges from rotationally resolved electronic spectroscopy of large molecules to nuclear magnetic resonance (NMR) spectroscopy of molecules, which are partially oriented in an anisotropic liquid‐crystalline environment. The application of both the genetic algorithm (GA) and the evolution strategy algorithm (ES) approaches for the assignment of complex spectra and the necessity of fitting meta parameters, which are not related to the parameters of the model describing the spectra are discussed. Examples for the possible applications comprise rovibronic spectra of various aromatic water clusters, rovibronic spectra of large hetero‐ and homo‐dimers, rovibrational spectra of the NH stretching vibrations in different tautomers of benzotriazole, and the NMR spectrum ofp‐bromo‐biphenyl dissolved in a nematic crystal.
High‐resolution Valence‐shell Photoionization
Authors: Pratt Stephen T.
Published: September 2011

This article presents a brief review of high‐resolution, valence‐shell photoionization studies of diatomic and small polyatomic molecules. Both single‐photon ionization of ground‐state molecules and multiphoton/multistep ionization of excited‐state molecules are discussed, and the complementary nature of the two approaches is emphasized. Although direct photoionization processes are discussed, the principal focus of the article is on resonance phenomena such as autoionization and predissociation, with a particular emphasis on the former. The various forms of autoionization are illustrated by using examples from recent work on H2, H3, N2, NO, CO2, and other molecules.
Fundamentals of Electronic Spectroscopy
Authors: Wörner Hans J. , Merkt Frédéric
Published: September 2011

The basic principles of electronic spectroscopy of atoms and molecules in the gas phase are presented. In the first part, the elementary concepts necessary to describe the electronic structure of atoms, diatomic molecules, and polyatomic molecules are introduced in a systematic manner, with an effort to classify the different interactions (electrostatic, spin–orbit, hyperfine) and types of motions (electronic, vibrational, rotational), which determine the energy level structures. In the second part, electronic transitions are discussed, with their spin‐rovibrational structures. Examples ranging from the simple band structure of\documentclass{article}\usepackage{amsmath}\usepackage{amssymb}\usepackage{amsbsy}\pagestyle{empty}\begin{document}$\rm{\Sigma}^{+}_{{{\rm u}}}\leftarrow \rm{\Sigma}_{{{\rm g}}}^{+}$\end{document}electronic transitions of homonuclear diatomic molecules to the highly complex band structure of polyatomic molecules subject to strong vibronic interactions are used to illustrate the richness of electronic spectra.
Orders of Magnitude and Symmetry in Molecular Spectroscopy
Authors: Oka Takeshi
Published: September 2011

Considerations of the order of magnitude and the symmetry of various intramolecular interactions form the foundation of molecular spectroscopy. They are related and they together make molecular spectroscopy transparent and tidy. In this chapter, they are discussed starting from the very fundamental. The order of magnitude has not been discussed in any previous textbooks of molecular spectroscopy. The symmetry has been discussed in many textbooks and discussions here are limited to the rotational and nuclear spin states and its application to forbidden rotational transitions and the stability of nuclear spin modifications (ortho‐, para‐ etc.).
Fundamental Symmetries and Symmetry Violations from High Resolution Spectroscopy
Authors: Quack Martin
Published: September 2011

After an introductory survey, we introduce the seven fundamental symmetries of physics in relation to the group of the molecular Hamiltonian and the current standard model of particle physics (SMPP). We discuss the relation of these symmetries to conservation laws and fundamentally nonobservable properties of nature with the example of parity violation. The particular importance of experiments on detecting symmetry breakings is outlined and the three distinct, basic concepts of symmetry breaking (spontaneous,de facto,de lege) are illustrated with the example of space inversion symmetry breaking and parity violation in chiral molecules. Similar conceptual situations are found for our understanding of the underlying physics of molecular chirality by various types of symmetry breakings, of the evolution of biomolecular homochirality and of irreversibility as breaking of time reversal symmetry. The current status of the quantitative theory of molecular parity violation in the framework of electroweak quantum chemistry is reviewed, including the change of order of magnitude, which was found in recent years and has since been confirmed repeatedly.

The concepts of high‐resolution spectroscopic experiments on parity violation in chiral molecules are discussed and the status of current attempts toward detecting molecular parity violation is summarized with particular emphasis on the possibilities of measuring time‐dependent parity violation in the exceptional (still hypothetical) unstable parity isomers of chiral molecules. The concept of successive symmetry breakings in the quantum dynamics of molecules is illustrated with the wide range of time‐scales for symmetry‐breaking processes ranging from femtoseconds in experiments on very fast intramolecular vibrational redistribution (IVR) to the theoretical times of seconds for molecular parity violation.

The role of approximate symmetries and conservation laws for our understanding of selection rules in spectroscopy and in chemical reaction dynamics is analyzed in some detail with the example of approximate parity and nuclear spin symmetry conservation in radiative and reactive molecular processes. This includes the use of permutation‐inversion symmetry groups in applications to spectroscopy and state‐selected chemical reactions. Statistical concepts for the description of molecular energy levels are presented for use in high‐resolution spectroscopy and chemical reactions in relation to symmetry properties.

We conclude with a summary of the current status of the following symmetries and their violations in spectroscopy and molecular dynamics: nuclear spin symmetry in chemical processes, space inversion symmetry and parity violation in chiral molecules, time reversal symmetry in intramolecular processes, and combined charge conjugation, parity, and time reversal (CPT) symmetry in relation to more fundamental aspects of time reversal and speculations on mass differences in chiral molecules and chiral neutrinos and their antimatter counterparts.
High‐resolution Infrared–Ultraviolet (IR–UV) Double‐resonance Spectroscopy of Biological Molecules
Authors: Stanca‐Kaposta E. Cristina , Simons John P.
Published: September 2011

Tunable infrared (IR) laser excitation of small biomolecules entrained in an expanding supersonic jet, or of biomolecular ions held in a cooled ion trap, provides a powerful means of isolating them at low temperatures in the gas phase and probing their vibrational spectroscopy at high resolution. Many alternative experimental strategies have been devised to achieve this. The article reviews their development and presents some representative benchmark examples of their application.
Room Temperature Multifunctional Organophosphorus Gels and Liquid Crystals
Authors: Romero‐Nieto Carlos , Marcos Mercedes , Merino Sonia , Barberá Joaquín , Baumgartner Thomas , Rodríguez‐López Julián
Published: September 2011

A new series of extended dithieno[3,2‐b:2',3'‐d]phospholes with dendritic and non‐dendritic architectures involving phenylenevinylene as well as Fréchet‐type dendrons is presented. Modification of the phosphorus center with Pd allows for the generation of a dimeric dendrimer with Pd‐center. The synthetic strategy employed balances the rigid main scaffold with the flexibility of the dendrons in order to keep control of supramolecular self‐organization features. All the structures show a high photoluminescence in both solution and solid state, which is further intensified via energy transfer from the dendrons to the core. In terms of self‐organization in solution, three of the derivatives which bear an extended phosphole unit as common moiety are able to gel a variety of organic solvents at room temperature independently from the nature of their substituents. Notwithstanding, the dimeric dendrimer with Fréchet‐type dendrons is only able to display gel properties at low temperature. All gels exhibit pronounced photoluminescence properties that can be tuned by variation of the solvent and the temperature. In absence of solvent, the phosphole derivatives exhibit, moreover, liquid‐crystalline mesomorphism features. While three of the compounds present stable and highly luminescent columnar hexagonal phases at room temperature, the fourth species was found to be crystalline in the thermal range up to its isotropic state. Finally as proof of concept, the multifunctionality of these materials is demonstrated in an electrochromic device.
Molecular Self‐Assembly at Solid Surfaces
Authors: Otero Roberto , Gallego José María , de Parga Amadeo L. Vázquez , Martín Nazario , Miranda Rodolfo
Published: September 2011

Self‐assembly, the process by which objects initially distributed at random arrange into well‐defined patterns exclusively due to their local mutual interactions without external intervention, is generally accepted to be the most promising method for large‐scale fabrication of functional nanostructures. In particular, the ordering of molecular building‐blocks deposited at solid surfaces is relevant for the performance of many organic electronic and optoelectronic devices, such as organic field‐effect transistors (OFETs), organic light‐emitting diodes (OLEDs) or photovoltaic solar cells. However, the fundamental knowledge on the nature and strength of the intermolecular and molecule‐substrate interactions that govern the ordering of molecular adsorbates is, in many cases, rather scarce. In most cases, the structure and morphology of the organic‐metal interface is not known and it is just assumed to be the same as in the bulk, thereby implicitly neglecting the role of the surface on the assembly. However, this approximation is usually not correct, and the evidence gathered over the last decades points towards an active role of the surface in the assembly, leading to self‐assembled structures that only in a few occasions can be understood by considering just intermolecular interactions in solid or gas phases. In this work we review several examples from our recent research demonstrating the apparently endless variety of ways in which the surface might affect the assembly of organic adsorbates.
On a sustainability interval index and its computation through global optimization
Authors: Conner Jeremy A. , Phillis Yannis A. , Manousiouthakis Vasilios I.
Published: September 2011

Prior sustainability models have taken exact basic indicator (BI) values of an entity's sustainability and computed an exact value of the entity's sustainability index. However, BI values are either uncertain or difficult to obtain. In this work, we propose a novel approach that transforms BI data in the form of intervals containing all possible BI values to an interval containing all possible values of the sustainability index. This interval is termed the “sustainability index interval” (SII). Computation of the SII is achieved through solution of a minimization and a maximization problem using global optimization techniques. Although the underlying global optimization problems are nonconvex, they are shown to possess a number of properties that can be utilized to reduce the burden associated with SII's computation. Based on these properties, a branch‐and‐bound algorithm is developed, which exactly quantifies the SII in a finite number of iterations. © 2011 American Institute of Chemical Engineers AIChE J, 2012
Effects of SCH 486757, A Nociceptin‐1 Receptor Agonist, on Fertility and Reproductive Hormone Levels in Female CRL:CD®[SD] Rats
Authors: Enright Brian P. , McIntyre Barry S. , Barat Stephen A. , Treinen Kimberley A. , Kopytek Stephan J.
Published: September 2011

BACKGROUND

SCH 486757 is a nociceptin‐1 receptor agonist that was in development as an antitussive. Studies were conducted to characterize its effects on female fertility and to examine its potential modes of action.

METHODS

Female rats were administered up to 20 mg/kg SCH 486757 before/during mating through gestation day (GD) 7; female fertility and embryonic development were assessed on GD 14. In a subsequent study, pregnant rats were dosed up to 50 mg/kg SCH 486757 from GD 0 to 7. Reproductive hormones were assessed on GD 1, 3, 5, and 7, and embryonic development was assessed on GD 14. A subset of dosed dams were allowed to deliver, were subsequently re‐mated, and reproductive hormones and fertility were assessed on GD 7 and 14, respectively. To determine the effects of SCH 486757 on nonpregnant rats, doses of up to 50 mg/kg SCH 486757 were administered for 4 days beginning on the day of estrus; reproductive hormones were assessed after the final dose.

RESULTS

Female rats administered ≥20 mg/kg SCH 486757 exhibited abnormal estrous cycles; decreased fertility, number of corpora lutea, and implantation sites; and increased pre‐ and postimplantation loss. In general, administration of SCH486757 was associated with lower luteinizing hormone (LH) progesterone (P4), and estradiol (E2) levels in pregnant rats. These effects on fertility/embryonic development and reproductive hormones exhibited reversibility post dosing. Nonpregnant rats in the 50‐mg/kg group exhibited apparent decreases in P4 and E2 levels, with no apparent effects on LH values.

CONCLUSIONS

The SCH 486757‐related effects on fertility and embryonic development were likely the result of decreases in P4, E2, and/or LH, rather than being due to decreased prolactin levels.