bluuebunny/crossref_metadata_2025 huggingface dataset:
HPVVaccines
Authors: Wilkinson Dianna E , Inglis Stephen
Published: January 2015

The discovery in the early 1970s that cervical cancer was caused by infection with human papillomavirus (HPV) stimulated a highly successful vaccine development programme based on the use of recombinant deoxyribonucleic acid (DNA) technology to produce virus proteins in a form that can stimulate powerful and long‐lasting antibody responses. The vaccines have been designed as combinations to target theHPVvirus types that are responsible for most human disease. Clinical trials have shown that it is possible to prevent both genital warts and the early stages of cervical cancer through vaccination and this has led to licensure and use ofHPVvaccines in many countries throughout the world. Progression from initial virus infection to development of invasive cancer is often very slow, however, and so it will be many years before the impact of the vaccine on the overall disease burden is fully understood.

Key Concepts

Vaccine development for HPV has been complex but highly successful. Successful vaccines were made by recombinant protein expression to produce virus‐like particles (VLPs).

Prevention of papillomavirus‐induced disease requires neutralising antibodies at the mucosal site of infection.

The main public health priority was to achieve high coverage in vaccinating women with the aim to prevent cervical cancer.

Prophylactic HPV vaccine efficacy has been remarkably high.

Some cross‐protection is observed between different vaccine types.

HPV vaccines have been implemented in populations of young women widely around the world.

Access to affordable HPV vaccines in poor countries is a key goal but remains a challenge.

The scope of HPV vaccination extends to the prevention of non‐cervical HPV infections and related diseases in both females and males.
Neural Prostheses
Authors: Kasten Michael R , Ievins Aiva M , Moritz Chet T
Published: January 2015

A neural prosthesis is a device that aims to restore or replace the functions of the nervous system that are lost to disease or injury. Examples include devices to improve hearing, vision, motor and cognitive functions. Neural prostheses artificially stimulate the nervous system to convey sensory information, activate paralysed muscles or modulate the excitability of neural circuits to improve conditions such as chronic pain, epilepsy or tremor. Some neuroprostheses also record activity from the nervous system, which can be useful for patients who have difficulty moving or communicating. These devices can decipher the intention of the user or detect ongoing brain events such as seizures by recording neural signals directly from the brain. Emerging neuroprostheses aim to ‘close the loop’ using recorded neural activity to control stimulation delivered elsewhere in the nervous system with the goal of improving function.

Key Concepts

Neural prostheses aim to replace lost function or control activity within the nervous system following injury or disease.

Sensory neural prostheses transduce external events (e.g. sound, light) into artificial stimulation delivered to the nervous system.

Motor neural prostheses aim to restore functional movement to weak or paralysed muscles.

Neuromodulatory devices utilise electrical stimulation to modulate the excitability of neural circuits to improve symptoms of neurological diseases such as pain, tremor and the occurrence of seizures.

Recording neuroprostheses aim to detect the user's intention or brain state in order to enable communication or control of external devices.

Closed‐loop neuroprostheses utilise neural recording to control functional or symptom‐relieving stimulation.

Methods are emerging for optical and magnetic stimulation of the nervous system to supplement the electrical stimulation techniques currently in use.
Multi‐component Plant Viruses
Authors: Zhang Xiao‐Feng , Qu Feng
Published: January 2015

Many plant viruses divide their coding capacity into multiple genomic segments, hence are referred to as multi‐component viruses. These include viruses with either RNA or DNA genomes, in either single‐stranded (ss) or double‐stranded (ds) conformations. Furthermore, those with ssRNA genomes may encode viral proteins on the genome strand ([+] sense RNA viruses), the complementary strand ([−] sense RNA viruses) of the genomic RNA or both (ambisense RNA viruses). Multi‐component, (+) sense RNA viruses could comprise up to five genome segments, whereas (−) sense RNA viruses can have up to eight. Strikingly, most of characterised dsRNA viruses have 10–12 genome segments packaged in the same virus particles. Finally, the genomes of multi‐component DNA plant viruses are almost always single‐stranded, circular, and each of the segments (up to eight) is packaged in separate particles. Possible evolutionary relationships between multi‐component viruses and their monopartite relatives are discussed.

Key Concepts

Plant virus genomes can be non‐segmented (monopartite) or segmented (multi‐partite).

Multi‐partite plant viruses can be found in almost all major plant virus families, with different genome materials (RNA or DNA) and configurations (single‐stranded or double‐stranded), and varying virion shapes.

Plant viruses with most genome segments are plant‐infecting reoviruses, containing 10–12 double‐stranded RNA segments package together in the same non‐enveloped, multi‐layer capsids.

Nanoviruses are small viruses with up to eight single‐stranded, circular DNA genomes separately packaged in isometric particles.
Renal Ciliopathies
Authors: Bergmann Carsten
Published: January 2015

Defects in centrosome and cilium function lead to phenotypically related syndromes called ciliopathies. Cilia are microtubule‐based antennae that detect and orchestrate extracellular stimuli. As environmental rheostats and cellular signalling centres, they mediate multiple pathways that if disrupted lead to early developmental defects and cancer. Cystic kidney disorders such as polycystic kidney disease (ADPKD/ARPKD) and nephronophthisis (NPHP) play a central role in the elucidation of ciliopathies, and practically, all cilia‐related disorders can show renal cysts. In addition, patients may present with extrarenal manifestations in other organs. An accurate genetic diagnosis is crucial for genetic counselling, prenatal diagnostics and the clinical management of patients and their families. The increasing number of genes that have to be considered in patients with ciliopathies is challenging to address by conventional techniques and largely benefits from next‐generation sequencing (NGS)‐based approaches.

Key Concepts

Polycystic kidney disease (PKD) constitutes the most common life‐threatening genetic disorder and affects about 10–15 million people worldwide.

The majority of patients with PKD harbour mutations in the typical genes for ARPKD and ADPKD; however, mutations in other genes can mimic PKD.

PKD paved the way for other cilia‐related disorders of which most can show renal cysts.

Renal ciliopathies are characterized by tremendous clinical and genetic heterogeneity.

Patients may present with extrarenal manifestations in other organs (e.g. liver cysts, heart defects, retinal degeneration, deafness and intracranial aneurysms).

The underlying genotype can usually be identified by next‐generation sequencing (NGS)‐based approaches that allow the parallel analysis of all disease genes.

An accurate genetic diagnosis is crucial for genetic counselling, prenatal diagnostics and clinical management (with early detection and treatment of complications).
Tumor Microenvironment Activated Photothermal Strategy for Precisely Controlled Ablation of Solid Tumors upon NIR Irradiation
Authors: Ju Enguo , Dong Kai , Liu Zhen , Pu Fang , Ren Jinsong , Qu Xiaogang
Published: January 2015

Photothermal ablation has provided emerging and promising opportunities to further potentiate the efficacy of postoperative chemotherapy of tumor. However, it still cannot achieve a high level of selectivity because extraneous photodamage along the optical path to the tumor is unavoidable as the result of the uncontrollable distribution of the photothermal agents. In addition, it is technically difficult to keep photoirradiation localizing only on cancer cells. In this report, a new strategy is introduced for precisely controlled ablation of tumor through tumor microenvironment activated near‐infrared (NIR) photothermal therapy. By taking advantage of the pH‐dependent light‐heat conversion property of Au@PANI nanoparticles, much higher photothermal effect at pH 6.5 than that at pH 7.4 is achieved. Therefore, in normal tissues and blood vessels, NIR irradiation cannot lead to a lethal temperature with little or no harm to normal cells. In contrast, in acidic tumor microenvironment, the photothermal effect is activated. Consequently, NIR irradiation can effectively kill cancer cells through local hyperthermia. Importantly, with the benefit of the internal and external control to switch on the photothermal ablation, the technical difficulty to precisely localize laser irradiation on tumor cells can be circumvented.
Palladium–Cobalt Nanotube Arrays Supported on Carbon Fiber Cloth as High‐Performance Flexible Electrocatalysts for Ethanol Oxidation
Authors: Wang An‐Liang , He Xu‐Jun , Lu Xue‐Feng , Xu Han , Tong Ye‐Xiang , Li Gao‐Ren
Published: January 2015

PdCo nanotube arrays (NTAs) supported on carbon fiber cloth (CFC) (PdCo NTAs/CFC) are presented as high‐performance flexible electrocatalysts for ethanol oxidation. The fabricated flexible PdCo NTAs/CFC exhibits significantly improved electrocatalytic activity and durability compared with Pd NTAs/CFC and commercial Pd/C catalysts. Most importantly, the PdCo NTAs/CFC shows excellent flexibility and the high electrocatalytic performance remains almost constant under the different distorted states, such as normal, bending, and twisting states. This work shows the first example of Pd‐based alloy NTAs supported on CFC as high‐performance flexible electrocatalysts for ethanol oxidation.
Antitumor Drug Delivery Modulated by A Polymeric Micelle with an Upper Critical Solution Temperature
Authors: Li Weishuo , Huang Liwen , Ying Xiaoying , Jian You , Hong Yuan , Hu Fuqiang , Du Yongzhong
Published: January 2015

Thermally sensitive polymeric nanocarriers were developed to optimize the release profile of encapsulated compounds to improve treatment efficiency. However, when referring to thermally sensitive polymeric nanocarriers, this usually means systems fabricated from lower critical solution temperature (LCST) polymers, which have been intensively studied. To extend the field of thermally sensitive polymeric nanocarriers, we for the first time fabricated a polymeric drug delivery system having an upper critical solution temperature (UCST) of 43 °C based on an amphiphilic polymer poly(AAm‐co‐AN)‐g‐PEG. The resulting polymeric micelles could effectively encapsulate doxorubicin and exhibited thermally sensitive drug release both in vitro and in vivo. A drastically improved anticancer efficiency (IC50 decreased from 4.6 to 1.6 μg mL−1, tumor inhibition rate increased from 55.6 % to 92.8 %) was observed. These results suggest that UCST‐based drug delivery can be an alternative to thermally sensitive LCST‐based drug delivery systems for an enhanced antitumor efficiency.
Addition of Ethylene or Hydrogen to a Main‐Group Metal Cluster under Mild Conditions
Authors: Vasko Petra , Wang Shuai , Tuononen Heikki M. , Power Philip P.
Published: January 2015

Reaction of the tin cluster Sn8(Ar)4 (Ar=C6H2‐2,6‐(C6H3‐2,4,6‐Me3)2) with excess ethylene or dihydrogen at 25 °C/1 atmosphere yielded two new clusters that incorporated ethylene or hydrogen. The reaction with ethylene yielded Sn4(Ar)4(C2H2)5 that contained five ethylene moieties bridging four aryl substituted tin atoms and one tin–tin bond. Reaction with H2 produced a cyclic tin species of formula (Sn(H)Ar)4, which could also be synthesized by the reaction of {(Ar)Sn(μ‐Cl)}2 with DIBAL‐H. These reactions represent the first instances of direct reactions of isolable main‐group clusters with ethylene or hydrogen under mild conditions. The products were characterized in the solid state by X‐ray diffraction and IR spectroscopy and in solution by multinuclear NMR and UV/Vis spectroscopies. Density functional theory calculations were performed to explain the reactivity of the cluster.
Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex
Authors: Ndoyom Victoria , Fusaro Luca , Dorcet Vincent , Boitrel Bernard , Le Gac Stéphane
Published: January 2015

Inspired by a Newton’s cradle device and interested in the development of redox‐controllable bimetallic molecular switches, a mixed‐valence thallium(III)/thallium(I) bis‐strap porphyrin complex, with TlIII bound out of the plane of the N core and TlI hung to a strap on the opposite side, was formed by the addition of TlOAc to the free base and exposure to indirect sunlight. In this process, oxygen photosensitization by the porphyrin allows the oxidation of TlI to TlIII. The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with TlIII funneling through the macrocycle. Further exposure of the complex to direct sunlight leads to thallium dissociation and to total recovery of the free base. Hence, the porphyrin plays a key role at all stages of the cycle of the complex: It hosts two metal ions, and by absorbing light, it allows the formation and dissociation of TlIII. These results constitute the basis for the further design of innovative light‐driven bimetallic molecular devices.
A Highly Stabilizing Silver(I)‐Mediated Base Pair in Parallel‐Stranded DNA
Authors: Sinha Indranil , Fonseca Guerra Célia , Müller Jens
Published: January 2015

The first parallel‐stranded DNA duplex with Hoogsteen base pairing that readily incorporates an Ag+ion into an internal mispair to form a metal‐mediated base pair has been created. Towards this end, the highly stabilizing6 FP‐Ag+‐6 FPbase pair comprising the artificial nucleobase 6‐furylpurine (6 FP) was devised. A combination of temperature‐dependent UV spectroscopy, CD spectroscopy, and DFT calculations was used to confirm the formation of this base pair. The nucleobase6 FPis capable of forming metal‐mediated base pairs both by the Watson–Crick edge (i.e. in regular antiparallel‐stranded DNA) and by the Hoogsteen edge (i.e. in parallel‐stranded DNA), depending on the oligonucleotide sequence and the experimental conditions. The6 FP‐Ag+‐6 FPbase pair within parallel‐stranded DNA is the most strongly stabilizing Ag+‐mediated base pair reported to date for any type of nucleic acid, with an increase in melting temperature of almost 15 °C upon the binding of one Ag+ion.
A robust and coarse surface mesh modified by interpenetrating polymer network hydrogel for oil‐water separation
Authors: Zhu Jinlong , Li Huili , Du Juan , Ren Wenchen , Guo Pingping , Xu Shimei , Wang Jide
Published: January 2015

A robust and coarse surface mesh was fabricated by introducing a hydrogel coating with interpenetrating polymer network (IPN) structure on stainless steel mesh. The IPN hydrogel was prepared by crosslinking polymerization of acrylic acid (AA) followed by condensation reaction of polyvinyl alcohol (PVA) and glutaraldehyde (GA) at room temperature. As a result, the roughness of modified mesh was enhanced obviously and oil droplet underwater showed a larger contact angle. The hydrogel‐coated surface showed an underwater superoleophobicity with an oil contact angle of 153.92 ± 1.08°. Besides, stable wettability was observed. The mesh can selectively separate oil from water with a high separation efficiency of above 99.8%. This work provides a facile method to strengthen the coating and enhance the efficiency of oil‐water separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41949.
DOPO‐VTS‐based coatings in the realm of fire retardants for cotton textile
Authors: Chernyy Sergey , Ulah Saif , Sørensen Gitte , Tordrup Sie Woldum , Pedersen Peter Bøgh , Almdal Kristoffer
Published: January 2015

The work elucidates the feasibility of incorporation of phosphorus‐silicon containing fire retardant (10‐(2‐trimethoxysilyl‐ethyl)‐9‐hydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide [DOPO‐VTS]) into nanosol coating solutions by cohydrolysis cocondensation reaction of DOPO‐VTS with tetraethoxysilane precursor (TEOS). Impregnation of cotton with the organophosphorus silane in a form of nanosol dispersion afforded better fire retardancy of such samples compared to pure DOPO or TEOS‐treated cotton indicating synergism between phosphorus and silicon containing species in a condensed phase. The detailed analysis by TGA‐MS and SEM pointed to the fact that DOPO‐VTS acts as a promoter of cotton degradation which, in turn, results in acceleration of the charring process and formation of compact char in contrast to TEOS‐treated samples. Further analysis of the char by XPS confirmed high content of carbonaceous residue in the case of DOPO‐VTS‐treated samples while mainly siliceous component was left in the char in case of cotton treated with TEOS. Standard flammability test (EN ISO 15025:2008) additionally confirmed the absence of smoldering and better overall fire performance of the DOPO‐VTS samples in contrast to TEOS‐treated samples. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41955.
Absorption and migration of bio‐based epoxidized soybean oil and its mixtures with tri(2‐ethylhexyl) trimellitate in poly(vinylchloride)
Authors: Mao Di , Chaudhary Bharat Indu , Sun Bin , Shen Chun‐Yin , Yuan Dong‐ming , Dai Gan‐Ce , Li Bin , Cogen Jeffrey M.
Published: January 2015

The efficacy of epoxidized soybean oil (ESO), tri(2‐ethylhexyl) trimellitate, and mixtures thereof as plasticizers for poly(vinylchloride) has been studied. At 80°C, the trimellitate was slower to absorb in this polymer than ESO and was also less soluble, but the former exhibited higher solubility at 120°C. Plasticization efficiencies of stabilized polymeric compositions were similar with ESO and the trimellitate (despite their very different molecular weights). The trimellitate yielded greater mass loss during heat aging of the plasticized compositions, but substituting even minor amounts of it with ESO decreased mass loss synergistically. The trimellitate also resulted in more of an increase in hardness than ESO over time at elevated temperatures, but when aged at 120°C, mixtures of the two surprisingly had more deleterious effects. Thus, although ESO can replace part or all of trimellitates in plasticized PVC, using it as sole plasticizer would be preferable when heat aging performance is a requirement. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41966.
CTLA‐4 blockade with ipilimumab: biology, safety, efficacy, and future considerations
Authors: Camacho Luis H.
Published: January 2015

Melanoma remains a critical public health problem worldwide. Patients with stage IV disease have very poor prognosis and their 1‐year survival rate is only 25%. Until recently, systemic treatments with a positive impact on overall survival (OS) had remained elusive. In recent years, the United States Food and Drug Administration (FDA) – approved several novel agents targeting the RAS/RAF/MEK/ERK pathway (vemurafenib, dabrafenib, and trametinib) – critical in cell division and proliferation of melanoma, and an immune checkpoint inhibitor (ipilimumab) directed against the cytotoxic T lymphocyte Antigen ‐ (CTLA‐4). Moreover, recent reports of clinical trials studying other immune checkpoint modulating agents will most likely result in their FDA approval within the next months. This review focuses on ipilimumab, its safety and efficacy, and future considerations. Ipilimumab has demonstrated a positive OS impact after a several‐year follow‐up. It is also recognized that due to its mechanism of action, the response patterns to ipilimumab can differ from those observed in patients following treatment with conventional cytotoxic agents and even the most recently approved BRAF inhibitors. Most patients (84.8%) experience drug‐related adverse events (AEs) of any grade; most of these are mild to moderate and immune mediated. However, a minority of patients may also experience severe and life‐threatening AEs. In clinical studies, AEs were managed according to guidelines that emphasized close clinical monitoring and early use of corticosteroids when appropriate. Preliminary results have taught us the potential greater toxicity when in combination with vemurafenib, and the greater antitumor efficacy when combined with nivolumab, a monoclonal antibody directed against programmed death receptor‐1 (PD‐1), another immune checkpoint inhibitor. Future challenges include the optimization of dosing and toxicities when used as a single agent, and studying the safety and efficacy of combinations with targeted small molecules and other monoclonal antibodies to treat patients with melanoma and other malignancies.
Triplex Crosslinking through Furan Oxidation Requires Perturbation of the Structured Triple‐Helix
Authors: Gyssels Ellen , Carrette Lieselot L. G. , Vercruysse Emma , Stevens Kristof , Madder Annemieke
Published: January 2015

Short oligonucleotides can selectively recognize duplexes by binding in the major groove thereby forming triplexes. Based on the success of our recently developed strategy for furan‐based crosslinking in DNA duplexes, we here investigated for the first time the use of the furan‐oxidation crosslink methodology for the covalent locking of triplex structures by an interstrand crosslink. It was shown that in a triplex context, although crosslinking yields are surprisingly low (to nonexistent) when targeting fully complementary duplexes, selective crosslinking can be achieved towards mismatched duplex sites at the interface of triplex to duplex structures. We show the promising potential of furan‐containing probes for the selective detection of single‐stranded regions within nucleic acids containing a variety of structural motifs.
Striking Antitumor Activity of a Methinium System with Incorporated Quinoxaline Unit Obtained by Spontaneous Cyclization
Authors: Bříza T. , Králová J. , Dolenský B. , Rimpelová S. , Kejík Z. , Ruml T. , Hajdúch M. , Džubák P. , Mikula I. , Martásek P. , Poučková P. , Král V.
Published: January 2015

A novel pentamethinium salt was synthesized with an unforeseen expanded conjugated quinoxaline unit directly incorporated into a pentamethinium chain. The compound exhibited high fluorescence intensity, selective mitochondrial localization, high cytotoxicity, and selectivity toward malignant cell lines, and resulted in remarkable in vivo suppression of tumor growth in mice.
Iridium(III)‐Catalyzed Benzylic Amine Directed CH Sulfonamidation of Arenes with Sulfonyl Azides
Authors: Chen Heng , Huestis Malcolm P.
Published: January 2015

The development of a benzylic amine directed ortho‐sulfonamidation of aryl CH bonds with sulfonyl azides was investigated. The combination of a commercially available iridium(III) complex with a silver salt gave rise to an active manifold capable of promoting efficient CN bond formation for a variety of substrates.
Unprecedented Ring–Ring Interconversion of N,P,C‐Cage Ligands
Authors: Villalba Franco José Manuel , Schnakenburg Gregor , Espinosa Ferao Arturo , Streubel Rainer
Published: January 2015

The novel N,P,C‐cage complexes5 a–fand6 a–fhave been obtained by the reaction of theP‐pentamethylcyclopentadienylphosphinidene complex2, generated thermally from 2H‐azaphosphirene complex1, withN‐methyl‐C‐arylcarbaldimines3 a–f. Li/Cl phosphinidenoid complex8reacted with3 a,bto give N,P,C‐cage complexes6 a,b, whereas with3 c–f, complexes6 c–fwere obtained in negligible amounts only. Both types of ligand N,P,C‐cage structures5and6were found to be in an unprecedented equilibrium, with5 a,fas the predominant species. Transient electrophilic terminal phosphinidene complexes10 a–fserve as intermediates in both ligand interconversions (5 a,f↔6 a,f), as evidenced through trapping reactions with phenylacetylene andN‐methyl‐C‐phenylcarbaldimine, thus leading to the novel N,P,C‐cage complexes13 band15. DFT calculations predicted a small difference in the relative energies of the two types of N,P,C‐cage ligands, and a remarkable stabilisation of the aminophosphinidene complex10as the common precursor, thereby providing an insight into this surprising 5‐ring–3‐ring interconversion. In depth analysis of intermediate10revealed the occurrence of both through‐bond (conventional inductive/mesomeric effects) and through‐space (non‐covalent interactions) mechanisms, which amount to 67.8 and 14.4 kcal mol−1, respectively, and account for the remarkable stabilisation of this intermediate.
Enantioselective Synthesis of All‐Carbon Quaternary Stereogenic Centers via Copper‐Catalyzed Asymmetric Allylic Alkylation of (Z)‐Allyl Bromides with Organolithium Reagents
Authors: Fañanás‐Mastral Martín , Vitale Romina , Pérez Manuel , Feringa Ben L.
Published: January 2015

A copper/phosphoramidite catalyzed asymmetric allylic alkylation of Z trisubstituted allyl bromides with organolithium reagents is reported. The reaction affords all‐carbon quaternary stereogenic centers in high yields and very good regio‐ and enantioselectivity. This systematic study illustrates the crucial role of the olefin geometry of the allyl substrate on the outcome of the reaction and provides a viable alternative to access these important structural motifs.
Synthesis of Small‐Sized, Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating
Authors: Yen Swee Kuan , Varma D. Prathyusha , Guo Wei Mei , Ho Vincent H. B. , Vijayaragavan Vimalan , Padmanabhan Parasuraman , Bhakoo Kishore , Selvan Subramanian Tamil
Published: January 2015

In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g−1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging.
Iron‐Catalyzed Diboration and Carboboration of Alkynes
Authors: Nakagawa Naohisa , Hatakeyama Takuji , Nakamura Masaharu
Published: January 2015

An iron‐catalyzed diboration reaction of alkynes with bis(pinacolato)diboron (B2pin2) and external borating agents (MeOB(OR)2) affords diverse symmetrical or unsymmetrical cis‐1,2‐diborylalkenes. The simple protocol for the diboration reaction can be extended to the iron‐catalyzed carboboration of alkynes with primary and, unprecedentedly, secondary alkyl halides, affording various tetrasubstituted monoborylalkenes in a highly stereoselective manner. DFT calculations indicate that a boryliron intermediate adds across the triple bond of an alkyne to afford an alkenyliron intermediate, which can react with the external trapping agents, borates and alkyl halides. In situ trapping experiments support the intermediacy of the alkenyl iron species using radical probe stubstrates.
Spectral compression using subspace clustering
Authors: Agahian Farnaz , Funt Brian
Published: January 2015

This article describes a subspace clustering strategy for the spectral compression of multispectral images. Unlike standard principal component analysis, this approach finds clusters in several different subspaces of different dimension. Consequently, instead of representing all spectra in a single low‐dimensional subspace of a fixed dimension, spectral data are assigned to multiple subspaces having a range of dimensions from one to eight. In other words, this strategy allows us to distribute spectra into different subspaces thereby obtaining the best fit for each. As a result, more resources can be allocated to those spectra that need many dimensions for accurate representation and fewer resources to those that can be modeled using fewer dimensions. For a given compression ratio, this trade off reduces the overall reconstruction error. In the case of compressing multispectral images, this initial compression method is followed by JPEG2000 compression in order to remove the spatial redundancy in the data as well. © 2015 Wiley Periodicals, Inc. Col Res Appl, 41, 7–15, 2016
Stacking of Metal Chelates with Benzene: Can Dispersion‐Corrected DFT Be Used to Calculate Organic–Inorganic Stacking?
Authors: Malenov Dušan P. , Ninković Dragan B. , Zarić Snežana D.
Published: January 2015

CCSD(T)/CBS energies for stacking of nickel and copper chelates are calculated and used as benchmark data for evaluating the performance of dispersion‐corrected density functionals for calculating the interaction energies. The best functionals for modeling the stacking of benzene with the nickel chelate are M06HF‐D3 with the def2‐TZVP basis set, and B3LYP‐D3 with either def2‐TZVP or aug‐cc‐pVDZ basis set, whereas for copper chelate the PBE0‐D3 with def2‐TZVP basis set yielded the best results. M06L‐D3 with aug‐cc‐pVDZ gives satisfying results for both chelates. Most of the tested dispersion‐corrected density functionals do not reproduce the benchmark data for stacking of benzene with both nickel (no unpaired electrons) and copper chelate (one unpaired electron), whereas a number of these functionals perform well for interactions of organic molecules.
Mechanism for the Nonadiabatic Photooxidation of Benzene to Phenol: Orientation‐Dependent Proton‐Coupled Electron Transfer
Authors: Chang Xue‐Ping , Cui Ganglong , Fang Wei‐Hai , Thiel Walter
Published: January 2015

An efficient catalytic one‐step conversion of benzene to phenol was achieved recently by selective photooxidation under mild conditions with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) as the photocatalyst. Herein, high‐level electronic structure calculations in the gas phase and in acetonitrile solution are reported to explore the underlying mechanism. The initially populated 1ππ* state of DDQ can relax efficiently through a nearby dark 1nπ* doorway state to the 3ππ* state of DDQ, which is found to be the precursor state involved in the initial intermolecular electron transfer from benzene to DDQ. The subsequent triplet‐state reaction between DDQ radical anions, benzene radical cations, and water is computed to be facile. The formed DDQH and benzene‐OH radicals can undergo T1→S0 intersystem crossing and concomitant proton‐coupled electron transfer (PCET) to generate the products DDQH2 and phenol. Two of the four considered nonadiabatic pathways involve an orientation‐dependent triplet PCET process, followed by intersystem crossing to the ground state (S0). The other two first undergo a nonadiabatic T1→S0 transition to produce a zwitterionic S0 complex, followed by a barrierless proton transfer. The present theoretical study identifies novel types of nonadiabatic PCET processes and provides detailed mechanistic insight into DDQ‐catalyzed photooxidation.
A New Self‐Report Inventory of Dyslexia for Students: Criterion and Construct Validity
Authors: Tamboer Peter , Vorst Harrie C. M.
Published: January 2015

The validity of a Dutch self‐report inventory of dyslexia was ascertained in two samples of students. Six biographical questions, 20 general language statements and 56 specific language statements were based on dyslexia as a multi‐dimensional deficit.

Dyslexia and non‐dyslexia were assessed with two criteria: identification with test results (Sample 1) and classification using biographical information (both samples). Using discriminant analyses, these criteria were predicted with various groups of statements. All together, 11 discriminant functions were used to estimate classification accuracy of the inventory. In Sample 1, 15 statements predicted the test criterion with classification accuracy of 98%, and 18 statements predicted the biographical criterion with classification accuracy of 97%. In Sample 2, 16 statements predicted the biographical criterion with classification accuracy of 94%. Estimations of positive and negative predictive value were 89% and 99%.

Items of various discriminant functions were factor analysed to find characteristic difficulties of students with dyslexia, resulting in a five‐factor structure in Sample 1 and a four‐factor structure in Sample 2. Answer bias was investigated with measures of internal consistency reliability.

Less than 20 self‐report items are sufficient to accurately classify students with and without dyslexia. This supports the usefulness of self‐assessment of dyslexia as a valid alternative to diagnostic test batteries. Copyright © 2015 John Wiley & Sons, Ltd.
Range of Validity of a Simplified Model for Diffuse Charge Dynamics
Authors: Li Mengying , Hu Howard H. , Bau Haim H.
Published: January 2015

The modelling of electrochemical processes often requires the solution of the Poisson‐Nernst‐Planck (PNP) equations. In complex geometries, such as porous electrodes, that is challenging due to the presence of disparate length scales, ranging from the Debye screening length (∼nm) to the device length scale (∼cm). To overcome this difficulty, one often assumes that the electric double layer (EDL) is at quasi‐equilibrium to construct a simplified model that accounts for ion diffusion in the electro‐neutral bulk of the electrolyte while replacing the EDLs with appropriate boundary conditions. Various researchers have demonstrated that such an approach is valid in the asymptotic limit of a thin EDL and moderate electrode potentials. In this note, we explore the range of validity of this approximation by considering a one‐dimensional electrolytic cell with blocking electrodes subjected to a step change and time‐periodic alternations in the electrodes’ potentials by calculating the errors associated with the approximate approach as functions of the EDL thickness and electric field frequency and intensity. Additionally, we delineate numerical instabilities associated with the numerical solutions of the bulk equations with the nonlinear boundary condition peculiar to this problem.
Assessment of CE‐ICP/MS hyphenation for the study of uranyl/protein interactions
Authors: Huynh Thi‐Ngoc Suong , Bourgeois Damien , Basset Christian , Vidaud Claude , Hagège Agnès
Published: January 2015

Identification of uranyl transport proteins is key to develop efficient detoxification approaches. Therefore, analytical approaches have to be developed to cope with the complexity of biological media and allow the analysis of metal speciation. CE‐ICP/MS was used to combine the less‐intrusive character and high separation efficiency of CE with the sensitive detection of ICP/MS. The method was based on the incubation of samples with uranyl prior to the separation. Electrophoretic buffers were compared to select a 10 mM Tris to 15 mM NaCl buffer, which enabled analyses at pH 7.4 and limited dissociation. This method was applied to the analysis of a serum. Two main fractions were observed. By comparison with synthetic mixtures of proteins, the first one was attributed to fetuin and in a lesser extent to HSA, and the second one to uranyl unbound to proteins. The analysis showed that fetuin was likely to be the main target of uranyl. CE‐ICP/MS was also used to investigate the behavior of the fetuin–uranyl complex, in the presence of carbonate, an abundant complexing agent of uranyl in blood. This method enabled association constants determination, suggesting the occurrence of both FETUA(UO22+) and FETUA(UO22+)(CO32−) complexes, depending on the carbonate concentration.
Searching for biomarkers of comorbidities in sera of treated HIV‐infected patients by isoelectric focusing
Authors: Malvoisin Etienne , Makhloufi Djamila , Livrozet Jean‐Michel
Published: January 2015

Based on their characteristics, we hypothesized that the following parameters, namely collagen IV, glutathione S‐transferase, secretory component (SC), and AMP‐activated protein kinase α1α2 may be useful serum markers in the detection of comorbidities in treated HIV‐infected patients. These parameters were determined in 204 HIV‐infected patients and 35 controls by using IEF and densitometry. Collagen IV was undetectable in controls and the majority of HIV‐infected patients. Twenty‐two HIV‐infected patients presented significantly elevated levels of collagen IV, most of them were coinfected with hepatitis C virus and/or hepatitis B virus. SC was undetectable in controls. SC was significantly increased in 81 HIV‐infected patients and significantly correlated with aspartate aminotransferase (r = 0.267, p = 0.0049), alkaline phosphatase (r = 0.309, p = 0.0011), and γ‐glutamyl‐transferase (r = 0.264, p = 0.0054). Glutathione S‐transferase levels of HIV‐infected patients were significantly higher than the controls (3779 ± 5860 vs. 785 ± 71 DU, p = 0.0007) and significantly correlated with serum urea (r = 0.204, p = 0.0038), triglycerides (r = 0.209, p = 0.0033), and lipase (r = 0.219, p = 0.0025). AMP‐activated protein kinase α1α2 levels of HIV‐infected patients were significantly higher than the controls (5676 ± 6248 vs. 1189 ± 6248 DU, p = 0.0009). Further studies are needed to demonstrate the relevance of these results to diagnose non‐AIDS‐related illnesses in HIV‐infected patients.
Love or fear: Can punishment promote cooperation?
Authors: Kroupa Sebestian
Published: January 2015

Cooperation is a paradox: Why should one perform a costly behavior only to increase the fitness of another? Human societies, in which individuals cooperate with genetically unrelated individuals on a considerably larger scale than most mammals do, are especially puzzling in this regard. Recently, the threat of punishment has been given substantial attention as one of the mechanisms that could help sustain human cooperation in such situations. Nevertheless, using punishment to explain cooperation only leads to further questions: Why spend precious resources to penalize free‐riders, especially if others can avoid this investment and cheaters can punish you back? Here, it is argued that current evidence supports punishment as an efficient means for the maintenance of cooperation, and that the gravity of proposed limitations of punishment for maintaining cooperation may have been overestimated in previous studies due to the features of experimental design. Most notably, the importance of factors as characteristic of human societies as reputation and language has been greatly neglected. Ironically, it was largely the combination of the two that enabled humans to shape costly punishment into numerous low‐cost and less detrimental strategies that clearly can promote human cooperation.
Unraveling the relationship between regional gray matter atrophy and pathology in connected white matter tracts in long‐standing multiple sclerosis
Authors: Steenwijk Martijn D. , Daams Marita , Pouwels Petra J.W. , J. Balk Lisanne , Tewarie Prejaas K. , Geurts Jeroen J. G. , Barkhof Frederik , Vrenken Hugo
Published: January 2015

Introduction

Gray matter (GM) atrophy is common in multiple sclerosis (MS), but the relationship with white matter (WM) pathology is largely unknown. Some studies found a co‐occurrence in specific systems, but a regional analysis across the brain in different clinical phenotypes is necessary to further understand the disease mechanism underlying GM atrophy in MS. Therefore, we investigated the association between regional GM atrophy and pathology in anatomically connected WM tracts.

Methods

Conventional and diffusion tensor imaging was performed at 3T in 208 patients with long‐standing MS and 60 healthy controls. Deep and cortical GM regions were segmented and quantified, and both lesion volumes and average normal appearing WM fractional anisotropy of their associated tracts were derived using an atlas obtained by probabilistic tractography in the controls. Linear regression was then performed to quantify the amount of regional GM atrophy that can be explained by WM pathology in the connected tract.

Results

MS patients showed extensive deep and cortical GM atrophy. Cortical atrophy was particularly present in frontal and temporal regions. Pathology in connected WM tracts statistically explained both regional deep and cortical GM atrophy in relapsing‐remitting (RR) patients, but only deep GM atrophy in secondary‐progressive (SP) patients.

Conclusion

In RRMS patients, both deep and cortical GM atrophy were associated with pathology in connected WM tracts. In SPMS patients, only regional deep GM atrophy could be explained by pathology in connected WM tracts. This suggests that in SPMS patients cortical GM atrophy and WM damage are (at least partly) independent disease processes. Hum Brain Mapp, 36:1796–1807, 2015. © 2015 Wiley Periodicals, Inc.
Making sense: Dopamine activates conscious self‐monitoring through medial prefrontal cortex
Authors: Joensson Morten , Thomsen Kristine Rømer , Andersen Lau M. , Gross Joachim , Mouridsen Kim , Sandberg Kristian , Østergaard Leif , Lou Hans C.
Published: January 2015

When experiences become meaningful to the self, they are linked to synchronous activity in a paralimbic network of self‐awareness and dopaminergic activity. This network includes medial prefrontal and medial parietal/posterior cingulate cortices, where transcranial magnetic stimulation may transiently impair self‐awareness. Conversely, we hypothesize that dopaminergic stimulation may improve self‐awareness and metacognition (i.e., the ability of the brain to consciously monitor its own cognitive processes). Here, we demonstrate improved noetic (conscious) metacognition by oral administration of 100 mg dopamine in minimal self‐awareness. In a separate experiment with extended self‐awareness dopamine improved the retrieval accuracy of memories of self‐judgment (autonoetic, i.e., explicitly self‐conscious) metacognition. Concomitantly, magnetoencephalography (MEG) showed increased amplitudes of oscillations (power) preferentially in the medial prefrontal cortex. Given that electromagnetic activity in this region is instrumental in self‐awareness, this explains the specific effect of dopamine on explicit self‐awareness and autonoetic metacognition. Hum Brain Mapp 36:1866–1877, 2015. © 2015 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc..
The intrinsic resting state voice network in Parkinson's disease
Authors: New Anneliese B. , Robin Donald A. , Parkinson Amy L. , Eickhoff Claudia R. , Reetz Kathrin , Hoffstaedter Felix , Mathys Christian , Sudmeyer Martin , Michely Jochen , Caspers Julian , Grefkes Christian , Larson Charles R. , Ramig Loraine O. , Fox Peter T. , Eickhoff Simon B.
Published: January 2015

Over 90 percent of patients with Parkinson's disease experience speech‐motor impairment, namely, hypokinetic dysarthria characterized by reduced pitch and loudness. Resting‐state functional connectivity analysis of blood oxygen level‐dependent functional magnetic resonance imaging is a useful measure of intrinsic neural functioning. We utilized resting‐state functional connectivity modeling to analyze the intrinsic connectivity in patients with Parkinson's disease within a vocalization network defined by a previous meta‐analysis of speech (Brown et al., 2009). Functional connectivity of this network was assessed in 56 patients with Parkinson's disease and 56 gender‐, age‐, and movement‐matched healthy controls. We also had item 5 and 18 of the UPDRS, and the PDQ‐39 Communication subscale available for correlation with the voice network connectivity strength in patients. The within‐group analyses of connectivity patterns demonstrated a lack of subcortical–cortical connectivity in patients with Parkinson's disease. At the cortical level, we found robust (homotopic) interhemispheric connectivity but only inconsistent evidence for many intrahemispheric connections. When directly contrasted to the control group, we found a significant reduction of connections between the left thalamus and putamen, and cortical motor areas, as well as reduced right superior temporal gyrus connectivity. Furthermore, most symptom measures correlated with right putamen, left cerebellum, left superior temporal gyrus, right premotor, and left Rolandic operculum connectivity in the voice network. The results reflect the importance of (right) subcortical nodes and the superior temporal gyrus in Parkinson's disease, enhancing our understanding of the neurobiological underpinnings of vocalization impairment in Parkinson's disease. Hum Brain Mapp 36:1951–1962, 2015. © 2015 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc.
Climate warming causes intensification of the hydrological cycle, resulting in changes to the vernal and autumnal windows in a northern temperate forest
Authors: Creed I. F. , Hwang T. , Lutz B. , Way D.
Published: January 2015

Climate warming is likely to lead to complex effects on northern forests of the temperate forest biome. We investigated whether rising temperatures altered the timing of snowmelt and snowpack accumulation or extended the forest growing season length in the Turkey Lakes Watershed in central Ontario. Archived satellite imagery was used to track changes in timing of snowpack loss/gain and canopy leaf on/off; the periods between these events were defined as the vernal (spring) and autumnal (fall) windows. We found only a slight extension of the growing season into the autumn period and no increase in the width of the vernal or autumnal windows, indicating that forest growth is not responding significantly to temperature increases during these windows. Archived time series of temperature, precipitation and discharge data for a nested set of catchments ranging in size from headwater (<10 ha) to regional (103 ha) catchments were used to track changes in the magnitude, timing and partitioning of precipitation into evapotranspiration and discharge. We found an intensification of hydrological cycling, with (1) a higher dryness index (PET/P) during the summer growing season and (2) earlier spring snowmelt discharges, and later more concentrated autumn storm discharges during the shoulder seasons. This intensification of the hydrological cycle during the summer growth season and the vernal and autumnal windows may not only limit opportunities for enhanced forest growth, but may be contributing to the recent observations of forest decline within this biome. Copyright © 2015 John Wiley & Sons, Ltd.
Adhesion and activation of platelets from subjects with coronary artery disease and apparently healthy individuals on biomaterials
Authors: Braune S. , Groß M. , Walter M. , Zhou S. , Dietze S. , Rutschow S. , Lendlein A. , Tschöpe C. , Jung F.
Published: January 2015

On the basis of the clinical studies in patients with coronary artery disease (CAD) presenting an increased percentage of activated platelets, we hypothesized that hemocompatibility testing utilizing platelets from healthy individuals may result in an underestimation of the materials' thrombogenicity. Therefore, we investigated the interaction of polymer‐based biomaterials with platelets from CAD patients in comparison to platelets from apparently healthy individuals. In vitro static thrombogenicity tests revealed that adherent platelet densities and total platelet covered areas were significantly increased for the low (polydimethylsiloxane, PDMS) and medium (Collagen) thrombogenic surfaces in the CAD group compared to the healthy subjects group. The area per single platelet—indicating the spreading and activation of the platelets—was markedly increased on PDMS treated with PRP from CAD subjects. This could not be observed for collagen or polytetrafluoroethylene (PTFE). For the latter material, platelet adhesion and surface coverage did not differ between the two groups. Irrespective of the substrate, the variability of these parameters was increased for CAD patients compared to healthy subjects. This indicates a higher reactivity of platelets from CAD patients compared to the healthy individuals. Our results revealed, for the first time, that utilizing platelets from apparently healthy donors bears the risk of underestimating the thrombogenicity of polymer‐based biomaterials. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 210–217, 2016.