bluuebunny/crossref_metadata_2025 huggingface dataset:
CalculatingNMRChemical Shifts andJ‐Couplings for Heavy Element Compounds
Authors: Autschbach Jochen
Published: September 2014

Ab initiocalculations of NMR parameters for compounds with heavy elements require a relativistic theoretical framework. Such calculations are able to reproduce experimentally observed ‘heavy atom’ effects in NMR spectroscopy quantitatively. Electron spin‐orbit (SO) coupling is a relativistic effect that leads to the ‘normal halogen dependence’ of light atom chemical shifts in the vicinity of heavy halogens. Similar effects exist for light atoms bound to heavy transition metals orf‐block elements or heavy main group elements other than halogens.J‐coupling constants involving heavy elements may increase by several hundred percent because of relativistic effects. The tensor properties of NMR shielding andJ‐coupling, observed routinely in solid‐state NMR, can be impacted very strongly by relativistic effects. This article discusses representative examples, provides a rationale why relativistic effects are large for atoms with high nuclear charges, and lists a selection of quantum chemistry program packages that are capable of relativistic NMR calculations.
Two‐Dimensional Correlation Spectroscopy: New Developments and Applications
Authors: Jung Young Mee , Noda Isao
Published: September 2014

This article outlines the recent progress in two‐dimensional (2D) correlation spectroscopy, especially new and noteworthy developments and its applications. 2D correlation spectroscopy is a powerful technique used to analyze effectively various spectral data, especially those obtained in various spectroscopic experiments. 2D correlation spectroscopy has undergone rapid developments. This article highlights new types of 2D correlation analysis, such as combination of chemometrics and 2D correlation spectroscopy, projection 2D analysis, and heterocorrelation analysis, as well as experimental practices, such as various perturbation methods, fields of applications, and analytical probes employed.
Regulatory Considerations of Biomanufacturing Facilities
Authors: Priesmeyer Kip
Published: September 2014

Throughout the design process, architectural engineer of biopharmaceutical facility must be cognizant of the various global and regional regulatory statutes, related regulations, and expectations that are applicable to the facility's design, form, and intended function. Regulatory aspects must be clearly understood, including design and construction features, open and closed processing and related area classifications, plumbing and lighting, equipment suitability, and the flow of personnel, equipment, and materials.

The chapter offers a regulatory “tool box” for a design team of a multiproduct biopharmaceutical facility. It provides an overview of US and European regulations and guidelines considering the quality systems and control strategies along with bioburden control, and their potential impact on the design and operation of a facility. A synopsis of the Compliance Program guidelines used by
FDA
(Food and Drug Administration) investigators who inspect biopharmaceutical facilities and the common
FDA
483 observations are included. The information given in this chapter should not be considered as all inclusive, but rather as a basic foundation in the attempt to achieve regulatory compliance during facility design.
Single Nucleotide Polymorphism
Authors: Børsting Claus , Pereira Vania , Andersen Jeppe D. , Morling Niels
Published: September 2014

Single nucleotide polymorphisms (SNPs) are the most frequent DNA sequence variations in the genome. They have been studied extensively in the last decade with various purposes in mind. In this chapter, we will discuss the advantages and disadvantages of using SNPs for human identification and briefly describe the methods that are preferred for SNP typing in forensic genetics. In addition, we will illustrate how SNPs can be used as investigative leads in the police investigation by discussing the use of ancestry informative markers and forensic DNA phenotyping. Modern DNA sequencing technologies (also callednext‐generation sequencingorNGS) have the potential to completely transform forensic genetic investigations as we know them today. Here, we will make a short introduction to NGS and explain how NGS may combine analysis of the traditional forensic genetic markers with analysis of SNPs. This will allow acquisition of more information from the sample materials and open up for new possibilities as well as new challenges.
Alternative Specimens—Sweat
Authors: de la Torre Fornell Rafael , Pichini Simona
Published: September 2014

Drugs are incorporated into sweat by passive diffusion and transdermal migration. The proof of principle of drug testing in sweat has been developed in the past 25 years. Numerous devices and approaches have been developed for the collection of sweat. The potential application of sweat analysis for on‐site drug testing at the roadside is limited by the nonavailability of adequate analytical devices. Their major limitation is the lack of sensitivity to some drug classes, an aspect that has been improving over the years. Adequate analytical methodology has been developed for drug analysis both in sweat patches and skin swabs. Immunoassays directed at the detection of parent drugs combined with highly sensitive chromatographic coupled to mass spectrometry analytical methods is the most common analytical approach. In particular, the sweat patch drug testing approach has been proven to be an alternative to urine testing in substance abuse treatment and probation programs. Some of the advantages include a wider detection window, easier sample collection, and reduced opportunities for sample tampering. There are still some pending studies on environmental skin contamination, drug absorption/loss through patch membrane, and drug reabsorption from patches that limit the routine application of drug testing in sweat to some extent.
Facial Comparison
Authors: Ruifrok Arnout
Published: September 2014

In general, people are thought to be reasonably good at recognizing faces. However, it is difficult to match images of unfamiliar faces: the process of facial comparison. Facial comparison is a wide‐ranging forensic technique: it involves disciplines such as image analysis, anatomy, anthropology, photogrammetry, 3D technology, statistics, and cognitive psychology (human as a measuring instrument). Many steps in the comparison process are still mediocre, poorly or not supported by scientific data. The issues “quantification of image quality,” “human as a measuring instrument,” and “individualizing value of features” will be discussed in the context of man and machine's functioning as a measuring instrument. Research on humans as a measuring instrument in facial comparison is limited; most of the research concerns “recognition” or “rapid” comparison. Performance of current automated biometric systems is still too low to be of use for forensic purposes, although biometric systems may be useful for automated investigation of standardized image databases. The evidential value of surveillance material is severely limited by the quality of most surveillance material.
Geographical Identification by Viral Genotyping
Authors: Ikegaya Hiroshi , Saukko Pekka J. , Katsumata Yoshinao , Takatori Takehiko
Published: September 2014

Illegal immigration and human trafficking in its various forms, including sale of both children and adults into forced labor, prostitution, or the buying or selling of human organs, are growing problems worldwide. These frequently result in fatalities in which the identity of the victim is often unknown and the individual can never be identified by the use of traditional forensic methods due to lack of antemortem data. A relatively recent survey among European Union (EU) countries, to which only eight countries responded, showed that of the total of 3035 unidentified human remains during the 5‐year period between 1994 and 1998, altogether 807 cadavers remained unidentified, suggesting that this is a growing problem that may have been underestimated by the authorities. Therefore, the forensic community has been looking for new indicators that might help in the identifying process.
DNA: An Overview
Authors: Graham Eleanor Alison May
Published: September 2014

Forensic DNA profiling has gone through several transformations since its initial conception to become the flexible and powerful technique that is used worldwide. By exonerating the innocent, implicating the guilty, identifying the deceased, and resolving paternity disputes, DNA profiling has forced its way to the forefront of public consciousness to become an almost ubiquitous part of criminal and civil investigations where the identity of key players is of importance. This article charts the history of DNA profiling, from the “Eureka” moment of Professor Sir Alec Jeffreys to contemporary technologies before introducing the key laboratory techniques required processing of biological samples from DNA extraction to profile production and interpretation.
Actinides: Organometallic Chemistry
Authors: Behrle Andrew C. , Walensky Justin R.
Published: September 2014

An actinide organometallic complex is one containing an actinide‐carbon σ‐bond, an actinide‐carbon π‐bond, or a combination of both. Actinide organometallic complexes are known for the actinide (An) elements from thorium through californium; the vast majority of the reports on organoactinide compounds, however, deal with thorium and uranium. The latter elements have isotopes, for example, thorium‐232 (t1/2 = 1.41 × 1010 years) and uranium‐238 (t1/2 = 4.468 × 109 years), with extremely long half‐lives. Modern organoactinide chemistry is characterized by the existence not only of actinide analogs to many classes of d‐transition metal complexes but also of increasingly common reports of compounds and types of reactions unique to the actinide series.
Photosynthesis
Authors: McIntosh Chelsea L. , Blankenship Robert E.
Published: September 2014

Photosynthesis is a biological process in which light energy is captured and stored as chemical energy by organisms such as plants, algae and certain bacteria. The stored energy is then used to power cellular processes. Most organisms that perform photosynthesis utilize chlorophylls or bacteriochlorophylls, in conjunction with other pigments such as carotenoids, pheophytins, and bilins. The emphasis in this article will be on the aspects of photosynthesis that relate most directly to the subject of bioinorganic chemistry. The aspects presented include excited states, photochemical reactions, the role of metal ions in photosynthesis, the structures of pigments, electron transfer pathways, reduction potentials of components, chromophore absorption and fluorescence spectra, energetics, and kinetics. Recent crystal structures of photosystems I and II, the important enzymes cytochrome bc1 and cytochrome b6f, and antenna complexes, supercomplexes, and recent megacomplexes are presented and discussed.
Cadmium: Coordination Chemistry
Authors: Borsari Marco
Published: September 2014

The coordinative behavior of cadmium(II) is typical of a soft acid. Evidence of this fact is its strong interactions with S
2
−
and HS
−
groups leading to the formation of highly stable complexes. Interactions with ligands containing oxygen‐donor groups are also well known. The chemistry of Cd
II
shows versatile coordination abilities, giving structures ranging from simple complexes to 1D, 2D, and 3D polymeric architectures. These polymers exhibit interesting physical properties. Cd
II
is able to substitute Zn
II
in the active site of several Zn‐enzymes and to interfere with the metabolism of Ca
II
. This is why a strong interest has been devoted in the past decade to the coordination chemistry of cadmium. The coordinative behavior of the cadmium(II) ion resembles that of mercury(II) and, in a lesser extent, of zinc(II). The main coordination numbers observed for Cd
II
are 4, 5, and 6. Owing to the larger size, Cd
II
assumes coordination number 6 more easily than Zn
II
. In CdMe
2
and dihalides in gas phase, Cd
II
only binds to two ligands, but in solid and solution phase, the coordination number is higher than 2. Coordination number 3 characterizes CdX
3
−
(X = halide) in organic media; however, in aqueous solution, CdBr
3
−
is pyramidal owing to the binding of one or more water molecules. Coordination numbers higher than 3 are observed in solid MCdX
3
. In aqueous solution, CdX
4
2
−
anions are tetracoordinated. Most CdX
2
L
2
complexes show a coordination number higher than 4, but a distorted tetrahedral geometry is found in CdX
2
L
2
when L is a P‐ or S‐donor. Cd
2+
is found to be five coordinated in CdCl
5
3
−
. A very large number of Cd compounds are six coordinated, for example, [Cd(H
2
O)
6
]
2+
, [Cd(acac)
2
], and [Cd(acac)
3
]
−
(acac = acetylacetonate) have a CdO
6
core. Six‐coordinated CdN
6
ions are formed with mono‐ and bidentate ligands such as imidazole or ethane‐1,2‐diamine. In the solid state, CdX
2
compounds are six coordinated. Halide adducts of the type CdX
4
L
2
are common; halogen bridging leads to an approximately octahedral Cd
II
for Cl
−
and Br
−
, but I
−
gives either four and five‐coordinated Cd
II
. A few seven‐coordinated compounds are known: in the solid state, each Cd
II
ion in [Cd(H
2
O)(CH
3
OC
6
H
4
COO)
2
]

n

is seven coordinated in a distorted pentagonal bipyramidal geometry. Eight coordination is rare. CdF
2
contains a CdF
8
core in a fluorite structure. In Cd(NO)
3
·4H
2
O, the four water molecules are square planar and bidentate NO
3
−
anions lie above and below this plane.
Structured Interviews of Experienced HUMINT Interrogators
Authors: Russano Melissa B. , Narchet Fadia M. , Kleinman Steven M. , Meissner Christian A.
Published: September 2014

The task force that led to the creation of the High‐Value Detainee Interrogation Group (HIG) recommended that the HIG fund a program of research aimed at establishing scientifically supported interrogative best practices. One of the ways to identify ‘best practices’ is to rely on direct reporting from subject‐matter experts. In this study, 42 highly experienced military and intelligence interrogators were interviewed about their interrogation‐related practices and beliefs, including such topics as training and selection, the role of rapport, perceptions regarding the techniques employed, lie detection, and the roles of interpreters and analysts. Interrogators indicated that excellent interpersonal skills on the part of an interrogator, an emphasis on rapport and relationship‐building techniques, and the assistance of well‐prepared interpreters and analysts are key components of a successful interrogation. It is our hope that the results of this study will stimulate research, influence training models, and ultimately contribute toward an interrogative best‐practice model. Copyright © 2014 John Wiley & Sons, Ltd.
Nanograined Half‐Heusler Semiconductors as Advanced Thermoelectrics: An Ab Initio High‐Throughput Statistical Study
Authors: Carrete Jesús , Mingo Natalio , Wang Shidong , Curtarolo Stefano
Published: September 2014

Nanostructuring has spurred a revival in the field of direct thermoelectric energy conversion. Nanograined materials can now be synthesized with higher figures of merit (ZT) than the bulk counterparts. This leads to increased conversion efficiencies. Despite considerable effort in optimizing the known and discovering the unknown, technology still relies upon a few limited solutions. Here ab initio modeling of ZT is performed for 75 nanograined compounds—the result of accurate distillation with electronic and thermodynamic filtering techniques from the 79 057 half‐Heusler entries available in the AFLOWLIB.org repository. For many of the compounds, the ZTs are markedly above those attainable with nanograined IV and III‐V semiconductors. About 15% of them may even outperform ZT ≈ 2 at high temperatures. This analysis elucidates the origin of the advantageous thermoelectric properties found within this broad material class. Machine learning techniques are used to unveil simple rules determining if a nanograined half‐Heusler compound is likely to be a good thermoelectric given its chemical composition.
Self‐reported physical work exposures and incident carpal tunnel syndrome
Authors: Dale Ann Marie , Gardner Bethany T. , Zeringue Angelique , Strickland Jaime , Descatha Alexis , Franzblau Alfred , Evanoff Bradley A.
Published: September 2014

Background

To prospectively evaluate associations between self‐reported physical work exposures and incident carpal tunnel syndrome (CTS).

Methods

Newly employed workers (n = 1,107) underwent repeated nerve conduction studies (NCS), and periodic surveys on hand symptoms and physical work exposures including average daily duration of wrist bending, forearm rotation, finger pinching, using vibrating tools, finger/thumb pressing, forceful gripping, and lifting >2 pounds. Multiple logistic regression models examined relationships between peak, most recent, and time‐weighted average exposures and incident CTS, adjusting for age, gender, and body mass index.

Results

710 subjects (64.1%) completed follow‐up NCS; 31 incident cases of CTS occurred over 3‐year follow‐up. All models describing lifting or forceful gripping exposures predicted future CTS. Vibrating tool use was predictive in some models.

Conclusions

Self‐reported exposures showed consistent risks across different exposure models in this prospective study. Workers' self‐reported job demands can provide useful information for targeting work interventions. Am. J. Ind. Med. 57:1246–1254, 2014. © 2014 Wiley Periodicals, Inc.
Using linked federal and state data to study the adequacy of workers' compensation benefits
Authors: Seabury Seth A. , Scherer Ethan , O'Leary Paul , Ozonoff Al , Boden Leslie
Published: September 2014

Background

We combined federal and state administrative data to study the long‐term earnings losses associated with occupational injuries and assess the adequacy of workers' compensation benefits.

Methods

We linked state data on workers' compensation claims from New Mexico for claimants injured from 1994 to 2000 to federal earnings records from 1987 to 2007. We estimated earnings losses up to 10 years after injury and computed the fraction of losses replaced by benefits.

Results

Workers with lost‐time injuries lost an average of 15% of their earnings over the 10 years after injury. On average, workers' compensation income benefits replaced 16% of these losses. Men and women had similar losses and replacement rates. Workers with minor injuries had lower losses but also had lower replacement rates.

Conclusion

Earnings losses after an injury are highly persistent, even for comparatively minor injuries. Income benefits replace a smaller fraction of those losses than previously believed. Am. J. Ind. Med. 57:1165–1173, 2014. © 2014 Wiley Periodicals, Inc.
Underreporting of musculoskeletal disorders in 10 regions in France in 2009
Authors: Rivière Stéphanie , Penven Emmanuelle , Cadéac‐Birman Hélène , Roquelaure Yves , Valenty Madeleine
Published: September 2014

Background

Underreporting of occupational diseases (OD) has been quantified, in particular in the United States, but little information is available in other countries. The aim of this study was to evaluate underreporting of musculoskeletal disorders (MSD) in France in 2009.

Methods

We calculated an indicator that approximated the underreporting rate of MSD in 10 regions of France. Two databases were used: data on OD compensated by insurance funding and data from the surveillance program for uncompensated work‐related diseases. Analyses were performed for carpal tunnel syndrome (CTS) and elbow, shoulder, and lumbar spine MSD.

Results

The underreporting rate was estimated at 59% (range 52–64%) for CTS, 73% (range 67–79%) for elbow MSD, 69% (range 63–74%) for shoulder MSD, and 63% (range 50–76%) for lumbar spine MSD.

Conclusions

This study revealed that MSD are substantially underreported in France, as in the United States, despite the differences in workers' compensation systems. Am. J. Ind. Med. 57:1174–1180, 2014. © 2014 Wiley Periodicals, Inc.
Application and implementation of the hazard risk matrix to identify hospital workplaces at risk for violence
Authors: Arnetz Judith E. , Hamblin Lydia , Ager Joel , Aranyos Deanna , Upfal Mark J. , Luborsky Mark , Russell Jim , Essenmacher Lynnette
Published: September 2014

Background

A key barrier to preventing workplace violence injury is the lack of methodology for prioritizing the allocation of limited prevention resources. The hazard risk matrix was used to categorize the probability and severity of violence in hospitals to enable prioritization of units for safety intervention.

Methods

Probability of violence was based on violence incidence rates; severity was based on lost time management claims for violence‐related injuries. Cells of the hazard risk matrix were populated with hospital units categorized as low, medium, or high probability and severity. Hospital stakeholders reviewed the matrix after categorization to address the possible confounding of underreporting.

Results

Forty‐one hospital units were categorized as medium or high on both severity and probability and were prioritized for forthcoming interventions. Probability and severity were highest in psychiatric care units.

Conclusions

This risk analysis tool may be useful for hospital administrators in prioritizing units for violence injury prevention efforts. Am. J. Ind. Med. 57:1276–1284, 2014. © 2014 Wiley Periodicals, Inc.
Acute symptoms associated with chemical exposures and safe work practices among hospital and campus cleaning workers: A pilot study
Authors: Lee Soo‐Jeong , Nam Bora , Harrison Robert , Hong OiSaeng
Published: September 2014

Background

Cleaning workers are regularly exposed to cleaning products containing hazardous chemicals. This study investigated acute symptoms associated with chemical exposures among cleaning workers and their safe work practices.

Methods

This cross‐sectional study included 183 cleaning workers employed in an academic medical center and affiliated health sciences campuses in Northern California. Data on respiratory, eye, skin, neurological, and gastrointestinal symptoms and occupational factors were collected by in‐person interviews or self‐administered questionnaires.

Results

Chemical‐related symptoms (several times monthly or more often) were more common among workers who performed patient area cleaning (44%) than hospital custodians (36%) or campus custodians (28%). After controlling for age, sex, and job title, symptoms were associated with exposure to carpet cleaners (OR = 2.98, 95% CI 1.28–6.92), spray products (OR = 2.82, 95% CI 1.16–6.82), solvents (OR = 2.71, 95% CI 1.20–6.15), and multi‐purpose cleaners (OR = 2.58, 935% CI 1.13–6.92). Except for gloves, regular use of personal protective equipment was infrequent.

Conclusions

Study findings suggest a need for additional interventions such as use of less toxic products to reduce health risks among cleaning workers. Am. J. Ind. Med. 57:1216–1226, 2014. © 2014 Wiley Periodicals, Inc.
Impact of differential injury reporting on the estimation of the total number of work‐related amputations
Authors: Tak Sangwoo , Grattan Kathleen , Boden Les , Ozonoff Al , Davis Letitia
Published: September 2014

Background

A capture‐recapture analysis was performed to estimate the total number of work‐related amputations. We examined the impact of misclassification due to differential injury reporting on the estimate of total number of work‐related amputations.

Methods

Bureau of Labor Statistics' Survey of Occupational Injuries and Illnesses (SOII) samples and workers' compensation records (WC) were used to estimate the total number of work‐related amputations. Some of the amputation cases in one data source matched with injuries other than amputations in the other data source. We performed sensitivity analyses reassigning such cases as matched amputations.

Results

Depending on how we treated the cases matched with other injuries, the total number of work‐related amputations ranged from 276 to 442 cases, yielding dramatically different capture rates (35–87%).

Conclusion

Due to differential classification, estimates of work‐related amputations would be biased. Our findings highlight the importance of accurately reporting and classifying work‐related injuries and illnesses. Am. J. Ind. Med. 57:1144–1148, 2014. © 2014 Wiley Periodicals, Inc.
Prognostic value of metabolic tumor volume as measured by fluorine‐18‐fluorodeoxyglucose positron emission tomography/computed tomography in nasopharyngeal carcinoma
Authors: Yoon Young‐Ho , Lee Seok‐Hwan , Hong Sung‐Lyong , Kim Seong‐Jang , Roh Hwan‐Jung , Cho Kyu‐Sup
Published: September 2014

Background

The prognostic value of the tumor burden characterized by the metabolic tumor volume (MTV) remains under investigation in nasopharyngeal carcinoma (NPC). The purpose of this study was to evaluate the prognostic value of the maximum standardized uptake value (SUVmax) and MTV according to metabolic volume threshold as measured by positron emission tomography (PET)/computed tomography (CT), and other clinical factors, in patients with NPC.

Methods

This study was a retrospective chart review. We evaluated the association of SUVmax, MTV2.5, MTV3.0, and other clinical factors with overall survival (OS) using Kaplan‐Meier and Cox regression models. (MTV2.5 and MTV3.0 are the volume of hypermetabolic tissue within the regions of gross tumor volumes with a SUV value greater than the threshold values of 2.5 and 3.0, respectively.)

Results

Higher MTV2.5 of 31.45 cm3 and MTV3.0 of 23.01 cm3 were associated with an increased risk of death (hazard ratio [HR] = 5.028; p = 0.029), although no significant relationship was found between SUVmax and OS. Interestingly, MTV3.0 was associated with OS in both the differentiated and undifferentiated groups, although MTV2.5 was only associated with OS in the undifferentiated group. Among the clinical parameters, only radiotherapy was associated with longer OS (HR = 12.124; p < 0.001).

Conclusion

The MTV and radiotherapy could be prognostic values associated with OS. Particularly, MTV2.5 and MTV3.0 might be valuable metabolic parameters for predicting long‐term survival in patients with NPC. Furthermore, MTV3.0 may be more useful because it can be applied irrespective of pathologic subtype.
How did that get there? A population‐based analysis of nasal foreign bodies
Authors: Svider Peter F. , Sheyn Anthony , Folbe Elana , Sekhsaria Vibhav , Zuliani Giancarlo , Eloy Jean Anderson , Folbe Adam J.
Published: September 2014

Background

The purpose of this study was to calculate nationwide incidence of emergency department (ED) visits for nasal foreign bodies, identify the most frequently encountered consumer products, and evaluate outcomes and demographic trends.

Methods

The Nationwide Electronic Injury Surveillance System (NEISS) was evaluated for ED visits related to nasal foreign bodies for the most recent 5‐year span available. Nationwide incidence was calculated, and the most frequent foreign bodies were identified and organized by demographics including age and gender.

Results

A total of 6418 entries extrapolated to an estimated 198,566 ED visits nationwide were found. Out of individual case entries evaluated, median patient age was 3 years, and 42.7% of patients were male. Ninety‐six percent (96.4%) of patients were released after examination/treatment. Jewelry beads comprised a plurality of nasal foreign bodies, followed by paper products and toys. Patients with nasal foreign bodies involving toys, building sets, pens/pencils, batteries, coins, and nails/screws were predominantly male, whereas patients with nasal foreign bodies involving jewelry, paper products, and buttons were predominantly female. Jewelry was the most common item for patients in most age groups; age‐specific differences in the composition of remaining nasal foreign bodies were noted.

Conclusion

A variety of consumer products carry inherent risks for becoming nasal foreign bodies, with nearly 200,000 ED visits over a 5‐year period. Jewelry beads, paper products, and toys were the most common products noted. Speedy recognition and retrieval of these items and other objects noted is imperative for avoidance of deleterious sequelae. Demographic‐specific trends noted and organized by age and gender may be an invaluable adjunct for patient history‐taking and clinical examination.
Absent CNKSR2 causes seizures and intellectual, attention, and language deficits
Authors: Vaags Andrea K. , Bowdin Sarah , Smith Mary‐Lou , Gilbert‐Dussardier Brigitte , Brocke‐Holmefjord Katja S. , Sinopoli Katia , Gilles Cindy , Haaland Tove B. , Vincent‐Delorme Catherine , Lagrue Emmanuelle , Harbuz Radu , Walker Susan , Marshall Christian R. , Houge Gunnar , Kalscheuer Vera M. , Scherer Stephen W. , Minassian Berge A.
Published: September 2014

Synaptic function is central to brain function. Understanding the synapse is aided by studies of patients lacking individual synaptic proteins. Common neurological diseases are genetically complex. Their understanding is likewise simplified by studies of less common monogenic forms. We detail the disease caused by absence of the synaptic protein CNKSR2 in 8 patients ranging from 6 to 62 years old. The disease is characterized by intellectual disability, attention problems, and abrupt lifelong language loss following a brief early childhood epilepsy with continuous spike‐waves in sleep. This study describes the phenotype of CNKSR2 deficiency and its involvement in systems underlying common neurological disorders. Ann Neurol 2014;76:758–764
Phonons and electron‐phonon coupling in graphene‐h‐BN heterostructures
Authors: Slotman Guus J. , de Wijs Gilles A. , Fasolino Annalisa , Katsnelson Mikhail I.
Published: September 2014

First principle calculations of the phonons of graphene‐h‐BN  heterostructures are presented and compared to those of the constituents. It is shown that AA and AB′ stacking are not only energetically less favoured than AB but also dynamically unstable. Low energy flat phonon branches of h‐BN character with out of plane displacement have been identified and their coupling to electrons in graphene has been evaluated.
De‐novo‐3D‐Strukturaufklärung mit Proteinmengen unter einem Milligramm mittels 100‐kHz‐MAS‐Festkörper‐NMR‐Spektroskopie
Authors: Agarwal Vipin , Penzel Susanne , Szekely Kathrin , Cadalbert Riccardo , Testori Emilie , Oss Andres , Past Jaan , Samoson Ago , Ernst Matthias , Böckmann Anja , Meier Beat H.
Published: September 2014

Die Festkörper‐NMR‐Spektroskopie gewinnt zunehmend an Bedeutung, wenn es um Strukturuntersuchungen von kristallinen, sich in Membranen befindlichen, sedimentierten oder fibrillären Proteinen geht. Bei vielen Untersuchungen werden allerdings typischerweise mehrere isotopenmarkierte Proben von 10–20 mg gebraucht. Wir zeigen hier, dass mit einem neuen NMR‐Probenkopf, der Rotationsfrequenzen um den magischen Winkel um 100 kHz erreicht, die Linienbreiten der Protonensignale verkleinert werden können. Unter ausschließlicher Verwendung von Strukturinformationen aus so gewonnenen Daten wurde eine gut definierte De‐novo‐Struktur des Modellproteins Ubiquitin mit zwei Proben zu je etwa 500 μg Protein erhalten. Damit ergeben sich neue Möglichkeiten für die Strukturbestimmung von Proteinen, die nur im Mikrogramm‐ oder zweistelligen Nanogrammbereich verfügbar sind. Dies sind typische Mengen für zum Beispiel eukaryotische Membranproteine, die in Organismen oder zellfrei exprimiert werden.
Colloidal Self‐Assembly of Catalytic Copper Nanoclusters into Ultrathin Ribbons
Authors: Wu Zhennan , Li Yanchun , Liu Jiale , Lu Zhongyuan , Zhang Hao , Yang Bai
Published: September 2014

Metal nanoclusters (NCs) with diameter below 2 nm are promising catalysts in oxygen reduction reactions (ORR). However, the high surface energy of ultra‐small clusters leads to structural instability, shedding doubt on practical applications. Herein, we demonstrate a self‐assembly method to improve the durability of catalytic metal NCs, employing copper NCs capped by 1‐dodecanethiol (DT) to form free‐standing ribbons in colloidal solution. By tuning the cooperation between the dipolar attraction between Cu NCs and the van der Waals attraction between DT, the thickness of ribbons is adjusted to a single NC scale. Such free‐standing ribbons exhibit excellent catalytic activity and durability in ORR.
Reaktionen in Nitroimidazol, ausgelöst durch niederenergetische (0–2 eV) Elektronen: Methylierung an N1‐H blockiert die Reaktivität
Authors: Tanzer Katrin , Feketeová Linda , Puschnigg Benjamin , Scheier Paul , Illenberger Eugen , Denifl Stephan
Published: September 2014

Niederenergetische Elektronen (NEEs) mit Energien unter 2 eV zersetzen 4‐Nitroimidazol (4NI) sehr effizient über dissoziative Elektronenanlagerung (DEA). Diese Reaktionen umfassen einfache Bindungsbrüche, aber auch komplexere Prozesse wie mehrfache Bindungsbrüche und die Bildung neuer Moleküle. Alle diese Reaktionen zeigen sich als scharfe Strukturen im detektierten Anionensignal und werden als Feshbach‐Resonanzen gedeutet, die effiziente Wegbereiter für DEA sind. Die außergewöhnlich vielfältigen chemischen Reaktionen von 4NI werden bei Methylierung von 4NI an der N1‐Position komplett blockiert. Diese bemerkenswerten Resultate haben auch Auswirkung auf die Entwicklung von Radiosensibilisatoren für die Strahlungstherapie von Tumoren auf Basis von Nitroimidazol.
Isomere des Dischwefeldinitrids, S2N2
Authors: Zeng Xiaoqing , Flores Antognini Andrea , Beckers Helmut , Willner Helge
Published: September 2014

Die UV‐Photolyse (λ=248 oder 255 nm) von cyclischem S2N2, das in fester Argonmatrix isoliert wurde, ergibt zwei offenschalige S2N2‐Isomere, trans‐SNSN (3A′′) und cis‐SNSN (3A′′), sowie das geschlossenschalige C2v‐symmetrische Dimer (SN)2 (1A1). Die neuartigen Isomere wurden über ihre IR‐Spektren und ihre wechselseitige photolytische Umwandlung charakterisiert. Quantenchemische Rechnungen stützen die experimentellen Ergebnisse und bieten Einblicke in die komplexe Potentialhyperfläche von S2N2.
Catalytic Consequences of the Thermodynamic Activities at Metal Cluster Surfaces and Their Periodic Reactivity Trend for Methanol Oxidation
Authors: Tu Weifeng , Chin Ya‐Huei (Cathy)
Published: September 2014

The periodic reactivity trend and the connection of kinetics to the thermodynamic activity of oxygen are established for the oxidation of methanol on metal clusters. First‐order rate coefficients are a single‐valued function of the O2‐to‐CH3OH ratio, because this ratio, together with the rate constants for O2 and CH3OH activation, determine the oxygen chemical potential, thus the relative abundance of active sites and bulk chemical state of the clusters. CH3OH activation rate constants on oxygen‐covered Ag, Pt, and Pd and on RuO2 clusters vary with the metal–oxygen binding strength in a classical volcano‐type relation, because the oxygen‐binding strength directly influences the reactivities of oxygen as H abstractors during the kinetically relevant CH3OH activation step. The differences in oxygen thermodynamic activity lead to five orders of magnitude variation in rates (Pt>Pd>RuO2>Ag, 373 K), because of its strong effects on the activation enthalpy and more prominently activation entropy in CH3OH activation.
Cu‐catalyzed coupling of arylsulfinic salts with arylsilanes under mild conditions
Authors: Yang Xiaomin , Cao Yanyan , Li Enbo , Zhang Pengmei , Hou Zhanzhong
Published: September 2014

Arylsilanes were efficiently coupled with arylsulfinic salts for the first time under mild conditions. Diarylsulfone derivatives were easily synthesized in high yields with the assistance of nitrogen‐containing ligands and KF. The transformation is simple and efficient and the starting materials are readily available. Copyright © 2014 John Wiley & Sons, Ltd.
Role of fluorinated monomer for simple demolding in nanoimprint lithography
Authors: Shin Min Jae , Shin Young Jae , Shin Jae Sup
Published: September 2014

In this study, we explored the effect of a fluorinated monomer on nanoimprint lithography (NIL) and determined the optimum amount of fluorinated monomer required in the formulation for better NIL. To estimate the role of the fluorinated monomer for demolding, NIL was conducted using copolymers of nonfluorinated silane monomers and fluorinated silane monomers. Epoxy ring‐opening photopolymerization based on the cationic polymerization mechanism was utilized for the NIL process. The physical properties of the photopolymerized copolymeric materials, such as tensile strength, elongation, modulus, and impact strength, as well as surface characteristics such as the contact angle were reported. Aluminum deposition on the nanoimprinted pattern, which is instrumental in fabricating a wire grid polarizer, was also conducted. According to the study results, the use of a copolymer containing 20 mol % of the fluorinated monomer in NIL proved to be the best formulation for easy demolding and for ensuring optimum levels of the physical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41317.
Preceramic polymer as precursor for near‐stoichiometric silicon carbon with high ceramic yield
Authors: Qian Xi , Zhou Quan , Ni LiZhong
Published: September 2014

Precursor polycarbosilane containing acetylenic and SiH group (PCAS) has been successfully prepared by the reaction of dilithioacetylene with methyl dichlorosilane, and characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, 1H‐NMR, 13C‐NMR, and 29Si‐NMR. Thermogravimetric analysis curve in nitrogen showed the temperature of 5 wt % weight losses (Td5) was 613°C, while the ceramic yield of PCAS was 88% at 1000°C. Pyrolysis behavior and structure evolution of the cured PCAS were studied by means of X‐ray diffraction, Raman, scanning electron microscope‐energy dispersive X‐ray spectrometer, transmission electron microscope (selected area electron diffraction and high resolution transmission electron microscope), and elemental analysis. The polymer to ceramic conversion was completed at 1600°C and the results revealed that the ceramic consisted of β‐SiC and α‐SiC. The composition of the ceramic was near‐stoichiometric with molar ratio of Si/C (1.02 : 1) except rare and localized free carbon inclusions. The SiC ceramics exhibited high thermo‐oxidation resistance at elevated temperatures in air atmosphere. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41335.
Real‐time property prediction for an industrial rubber‐mixing process with probabilistic ensemble Gaussian process regression models
Authors: Liu Yi , Gao Zengliang
Published: September 2014

In internal rubber‐mixing processes, data‐driven soft sensors have become increasingly important for providing online measurements for the Mooney viscosity information. Nevertheless, the prediction uncertainty of the model has rarely been explored. Additionally, traditional viscosity prediction models are based on single models and, thus, may not be appropriate for complex processes with multiple recipes and shifting operating conditions. To address both problems simultaneously, we propose a new ensemble Gaussian process regression (EGPR)‐based modeling method. First, several local Gaussian process regression (GPR) models were built with the training samples in each subclass. Then, the prediction uncertainty was adopted to evaluate the probabilistic relationship between the new test sample and several local GPR models. Moreover, the prediction value and the prediction variance was generated automatically with Bayesian inference. The prediction results in an industrial rubber‐mixing process show the superiority of EGPR in terms of prediction accuracy and reliability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41432.
Comparison of tensile and compressive characteristics of intra/interply hybrid laminates reinforced high‐density flexible foam composites
Authors: Yan Ruosi , Wang Rui , Lou Ching‐Wen , Lin Jia‐Horng
Published: September 2014

The current study focused on fabrication and mechanical evaluation of intra/interply hybrid laminates–reinforced high‐density flexible foam composites. The effects of composite thickness and expansion factor on the tensile and compressive characterization of the hybrid‐laminated composites were experimentally investigated. Double face sheets were made of high‐strength intra/interply hybrid laminates containing recycled Kevlar nonwovens and glass woven fabric. The results revealed that the hybrid laminates face sheet apparently promoted the tensile strength and tear resistance of the high‐density flexible polyurethane foam. Tearing resistance in perpendicular direction exceeded more than twice the value in parallel direction. In terms of dynamic cushioning properties, cushioning force increased with the increase in composite thickness and the decrease in expansion factor, whereas the cushioning capacity loss, however, showed a different trend with the variation of the parameters. Most samples buffered more than 95% incident force under dynamic loading. Composite thickness and expansion factor exhibited significant influence on compression and indentation properties, including hardness, initial hardness factor, and indentation modulus. Except the composites with 10 mm thickness, the intra/interply hybrid laminated composites exhibited hysteresis loss of indentation force deflection ranging from approximately 30 to 38%, which was due to the fiber and thermal bonding point failure of hybrid laminates as unrecoverable damage. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41438.
Synthesis and Biological Evaluation of tert‐Butyl‐5‐methylpyrimidin‐piperazine Derivatives as Anti‐Obesity Agents
Authors: Chen Jinying , Pu Yuzhi , Pei Heying , He Linhong , Fu Suhong , Chen Lijuan
Published: September 2014

A series of tert‐butyl‐5‐methylpyrimidin‐piperazine derivatives were synthesized and their anti‐obesity activities were evaluated. Compounds 4g and 5j were found to have significant effects in down‐regulating the triglyceride level of 3T3‐L1 adipocytes. 5j exhibited remarkable therapeutic effects on the diet‐induced obesity (DIO) mouse model at 20 mg kg−1 day−1 for 4 weeks by decreasing the weights of body, liver, and fat. 5j also regulated serum biomarkers to appropriate ranges, exerted therapeutic activity of steatosis in liver tissue and ameliorated the obese‐related symptoms. In addition, 5j significantly decreased the blood glucose levels in oral glucose tolerance tests and improved the insulin sensitivity in insulin tolerance tests. These results suggest that 5j could be a candidate for obesity treatment.
Altered Functional Magnetic Resonance Imaging Responses to Nonpainful Sensory Stimulation in Fibromyalgia Patients
Authors: López‐Solà Marina , Pujol Jesus , Wager Tor D. , Garcia‐Fontanals Alba , Blanco‐Hinojo Laura , Garcia‐Blanco Susana , Poca‐Dias Violant , Harrison Ben J. , Contreras‐Rodríguez Oren , Monfort Jordi , Garcia‐Fructuoso Ferran , Deus Joan
Published: September 2014

Objective

Fibromyalgia (FM) is a disorder characterized by chronic pain and enhanced responses to acute noxious events. However, the sensory systems affected in FM may extend beyond pain itself, as FM patients show reduced tolerance to non‐nociceptive sensory stimulation. Characterizing the neural substrates of multisensory hypersensitivity in FM may thus provide important clues about the underlying pathophysiology of the disorder. The aim of this study was to characterize brain responses to non‐nociceptive sensory stimulation in FM patients and their relationship to subjective sensory sensitivity and clinical pain severity.

Methods

Functional magnetic resonance imaging (MRI) was used to assess brain response to auditory, visual, and tactile motor stimulation in 35 women with FM and 25 matched controls. Correlation and mediation analyses were performed to establish the relationship between brain responses and 3 types of outcomes: subjective hypersensitivity to daily sensory stimulation, spontaneous pain, and functional disability.

Results

Patients reported increased subjective sensitivity (increased unpleasantness) in response to multisensory stimulation in daily life. Functional MRI revealed that patients showed reduced task‐evoked activation in primary/secondary visual and auditory areas and augmented responses in the insula and anterior lingual gyrus. Reduced responses in visual and auditory areas were correlated with subjective sensory hypersensitivity and clinical severity measures.

Conclusion

FM patients showed strong attenuation of brain responses to nonpainful events in early sensory cortices, accompanied by an amplified response at later stages of sensory integration in the insula. These abnormalities are associated with core FM symptoms, suggesting that they may be part of the pathophysiology of the disease.
Altered Cellular and Humoral Immunity to Varicella‐Zoster Virus in Patients With Autoimmune Diseases
Authors: Rondaan Christien , de Haan Aalzen , Horst Gerda , Hempel J. Cordelia , van Leer Coretta , Bos Nicolaas A. , van Assen Sander , Bijl Marc , Westra Johanna
Published: September 2014

Objective

Patients with autoimmune diseases such as systemic lupus erythematosus (SLE) and granulomatosis with polyangiitis (Wegener's) (GPA) have a 3–20‐fold increased risk of herpes zoster compared to the general population. The aim of this study was to evaluate if susceptibility is due to decreased levels of cellular and/or humoral immunity to the varicella‐zoster virus (VZV).

Methods

A cross‐sectional study of VZV‐specific immunity was performed in 38 SLE patients, 33 GPA patients, and 51 healthy controls. Levels of IgG and IgM antibodies to VZV were measured using an in‐house glycoprotein enzyme‐linked immunosorbent assay (ELISA). Cellular responses to VZV were determined by interferon‐γ (IFNγ) enzyme‐linked immunospot (ELISpot) assay and carboxyfluorescein succinimidyl ester (CFSE) dye dilution proliferation assay.

Results

Levels of IgG antibodies to VZV were increased in SLE patients as compared to healthy controls, but levels of IgM antibodies to VZV were not. Antibody levels in GPA patients did not differ significantly from levels in healthy controls. In response to stimulation with VZV, decreased numbers of IFNγ spot‐forming cells were found among SLE patients (although not GPA patients) as compared to healthy controls. Proliferation of CD4+ T cells in response to stimulation with VZV was decreased in SLE patients but not GPA patients.

Conclusion

SLE patients have increased levels of IgG antibodies against VZV, while cellular immunity is decreased. In GPA patients, antibody levels as well as cellular responses to VZV were comparable to those in healthy controls. These data suggest that increased prevalence of herpes zoster in SLE patients is due to a poor cellular response. Vaccination strategies should aim to boost cellular immunity against VZV.