bluuebunny/crossref_metadata_2025_split huggingface dataset:
Modification of Antigen Impacts on Memory Quality after Adenovirus Vaccination
Authors: Colston Julia M. , Bolinger Beatrice , Cottingham Matthew G. , Gilbert Sarah , Klenerman Paul 
Published: March 2016

Abstract
The establishment of robust T cell memory is critical for the development of novel vaccines for infections and cancers. Classical memory generated by CD8+ T cells is characterized by contracted populations homing to lymphoid organs. T cell memory inflation, as seen for example after CMV infection, is the maintenance of expanded, functional, tissue-associated effector memory cell pools. Such memory pools may also be induced after adenovirus vaccination, and we recently defined common transcriptional and phenotypic features of these populations in mice and humans. However, the rules that govern which epitopes drive memory inflation compared with classical memory are not fully defined, and thus it is not currently possible to direct this process. We used our adenoviral model of memory inflation to first investigate the role of the promoter and then the role of the epitope context in determining memory formation. Specifically, we tested the hypothesis that conventional memory could be converted to inflationary memory by simple presentation of the Ag in the form of minigene vectors. When epitopes from LacZ and murine CMV that normally induce classical memory responses were presented as minigenes, they induced clear memory inflation. These data demonstrate that, regardless of the transgene promoter, the polypeptide context of a CD8+ T cell epitope may determine whether classical or inflating memory responses are induced. The ability to direct this process by the use of minigenes is relevant to the design of vaccines and understanding of immune responses to pathogens.
Synthesis of 4,4‐Dimethoxybut‐1‐Yne
Authors: Deng James , Wang Yu‐Pu , Danheiser* Rick L. 
Published: March 2016

Abstract
4,4‐Dimethoxybut‐1‐yne is a valuable difunctional synthetic building block which incorporates a masked aldehyde carbonyl group and terminal alkyne within a four‐carbon chain. To date this versatile synthon has found application as a key intermediate in the synthesis of heterocyclic compounds, functionalized alkenes, and several classes of biomolecules including carbohydrates, polyketides, and lipids. This article reports an efficient route to the formation of 4,4‐dimethoxybut‐1‐yne, which was employed as a key building block in the tandem benzannulation/cyclization strategy for the synthesis of highly substituted indoles developed.
Preparation of Crystalline (Diisopinocampheyl)Borane
Authors: Abbott Jason R. , Allais Christophe , Roush* William R. 
Published: March 2016

Abstract

(Diisopinocampheyl)borane ((Ipc)
2
BH) is a useful chiral organoborane reagent for asymmetric synthesis. (Ipc)
2
BH has been widely used in hydroboration reactions with alkenes leading, after oxidation of the resulting B–C, bond to enantioenriched secondary alcohols. This article describes the significant enhancement of enantiomeric purity of (Ipc)
2
BH, to 97% ee, in comparison to the considerably lower enantiomeric purity of the commercially available, inexpensive (α)‐pinene starting materials.
Palladium‐Catalyzed β‐Selective

C(sp
3
)–H

Arylation of
N
‐Boc‐Piperidines
Authors: Millet Anthony , Baudoin*1 Olivier 
Published: March 2016

Abstract

3‐Arylpiperidines are important building blocks in pharmaceutical research. They are usually synthesized through the construction of the piperidine ring or the reduction of a 3‐arylpyridine precursor, because the inert character of the C–H bonds in β‐position to the nitrogen atom is commonly thought to preclude direct β‐functionalization. Palladium‐catalyzed migrative Negishi coupling was developed to directly access 3‐aryl‐
N
‐Boc‐piperidines in good to excellent selectivity, and with yields between 43 and 76%. The design of a new flexible phenylpyrrole‐based phosphine ligand proved to be a key element to induce both efficiency and β‐selectivity.
Preparation of Mono‐Cbz Protected Guanidines
Authors: Kwon Kihyeok , Haussener Travis J. , Looper* Ryan E. 
Published: March 2016

AbstractThe article discusses the synthesis of mono‐N‐acylguanidines, via acylation with acid chlorides or anhydrides is often complicated by over acylation due to the increased acidity of the initially formed mono‐N‐acylguanidine. Alternatively they can be accessed by the controlled hydrolysis of diacyl‐protected guanidines. Several methods have also been developed for their synthesis fromN‐acyl‐thioureas orN‐acyl‐pseudothioureas. The use of the monoprotected versions of the pyrazole transfer reagent have also been reported, but are unreactive or poorly reactive toward amines because of their decreased electrophilicity. The differentially protected pyrazole transfer reagent can be employed followed by removal of the Boc or Cbz protecting group.
Copper(
II
) Triflate as Additive in Low Loading
Au(I)
‐Catalyzed Hydroalkylation of Unactivated Alkenes
Authors: Fang Weizhen , Presset Marc , Guérinot Amandine , Bour Christophe , Bezzenine‐Lafollée* Sophie , Gandon* Vincent 
Published: March 2016

Abstract

The use of copper salts as additives in Au(I)‐catalyzed reactions allows the gradual delivery of [LAu]
+
from a reservoir of stable LAuX. With the Au/Cu catalytic system, it becomes possible to carry out gram‐scale reactions in a small amount of solvent, even at elevated temperature, without observing the formation of Au(0). Since then, we have worked on the scope of this Au/Cu catalytic system. The practical features of this method, including its operational simplicity, make it an expedient alternative to traditional methods.
Ruthenium‐Catalyzed Direct Oxidative Alkenylation of Arenes Through Twofold CH Bond Functionalization in Water: Synthesis of Ethyl (E)‐3‐(2‐Acetamido‐4‐Methylphenyl)Acrylate
Authors: Wang Lianhui , Rauch Karsten , Lygin Alexander V. , Kozhushkov Sergei I. , Ackermann* Lutz 
Published: March 2016

AbstractThe article discusses the synthesis of ethyl (E)‐3‐(2‐acetamido‐4‐methylphenyl)acrylate. Tremendous development in direct olefinations through twofold C–H bond functionalization of arenes and heteroarenes with readily accessible, selective, and rather inexpensive ruthenium catalysts have witnessed. Ruthenium(II)‐catalyzed oxidative alkenylations (a) of benzanilides and benzoic acids, (b) with electron‐withdrawing/ donating coordinating substituents, (c) with heterocyclic directing groups and (d) with heteroarenes have discussed.
Synthesis of Phosphoryl Ynamides by Copper‐Catalyzed Alkynylation of Phosphoramidates. Preparation of Diethyl Benzyl(oct‐1‐yn‐1‐yl)phosphoramidate
Authors: Read John M. , Wang Yu‐Pu , Danheiser* Rick L. 
Published: March 2016

Abstract

The article has focused on the application of
N
‐phosphoryl ynamides in [2 + 2] cycloadditions with ketenes where we have observed their reaction to occur at a rate as much as an order of magnitude faster than that of the corresponding
N
‐carbomethoxy ynamides. Synthesis of phosphoramidate by reaction of benzylamine with an iodophosphate generated in situ via the modified Todd‐Atherton procedure introduced by Mielniczak and Łopusinski. Synthesis of ynamides via copper‐promoted coupling of haloalkynes with several classes of amide derivatives. The extension of this chemistry to the
N
‐alkynylation of phosphoramidates was introduced by Hsung and coworkers in 2011 and provides a convenient and efficient method for the preparation of this class of ynamides.
Synthesis of 2‐Azido‐1,3‐Dimethylimidazolinium Hexafluorophosphate (
ADMP
)
Authors: Kitamura* Mitsuru , Murakami Kento 
Published: March 2016

Abstract
2‐Azido‐1,3‐dimethylimidazolinium hexafluorophosphate (ADMP) is safe and stable crystalline solid, and show efficient diazo‐transfer ability to primary amines. ADMP is not very hygroscopic and can be stored in a freezer (at –10 °C) for at least two months. Impact sensitivity tests and friction sensitivity tests showed that ADMP is not explosive in the test ranges. The exothermic decomposition of ADMP was observed through differential scanning calorimetry experiments from approximately 200 °C. These results suggest that ADMP can be safely used below its decomposition temperature, preferably below 100 °C in order to allow an appropriate safety margin.
Palladium‐Catalyzed Buchwald‐Hartwig Amination and Suzuki‐MiyauraCross‐Coupling Reaction of Aryl Mesylates
Authors: Wong Shun Man , Choy Pui Ying , Yuen On Ying , So* Chau Ming , Kwong* Fuk Yee 
Published: March 2016

Abstract
This report discusses the synthesis and applications of CM‐phos, which showed excellent catalytic activities towards the first palladium‐catalyzed amination and Suzuki coupling reaction of aryl mesylates. Aryl mesylates can be easily accessed from phenols, owing to their lower molecular mass, and cross‐coupling reactions utilizing these reagents have the advantage of higher atom economy than those employing the corresponding aryl tosylates. However, their relatively inert leaving‐group activity, with respect to tosylates, has limited their applications in coupling reactions. Thus, this area remains highly challenging as mesylates are regarded as the least active sulfonate leaving group.
Zirconium (
IV
) Chloride Catalyzed Amide Formation From Carboxylic Acid and Amine: (
S
)‐
tert
‐Butyl 2‐(Benzylcarbamoyl)Pyrrolidine‐1‐Carboxylate
Authors: Tinnis1 Fredrik , Lundberg1 Helena , Kivijärvi1 Tove , Adolfsson1* Hans 
Published: March 2016

Abstract

The procedure described herein is a direct amide coupling of nonactivated carboxylic acids and amines catalyzed by zirconium (IV) chloride. The amide functionality is of major importance in many scientific areas, for example in material science, chemistry, and biology. The amide functionality is one of the most synthesized within the pharmaceutical industry, and it has been estimated that 25% of the pharmaceutical compounds available on the market contain at least one amide bond. The importance of the amide bond is further emphasized by the fact that 2/3 of 128 drug candidates covered in a survey from Process Chemistry R&D departments of GlaxoSmithKline, AstraZeneca and Pfizer in 2006 made use of amide couplings. This method described is a mild and selective metal‐catalyzed protocol, giving rise to high yields of the desired products at moderate reaction temperatures, and without racemizing chiral amino acids. The method stems from our recent work where we have shown that early transition metal complexes such as ZrCl
4
or Ti(OPr

i

)
4
are excellent catalysts for a range of substrates, including the formation of both secondary and tertiary amides, as well as chiral amides.
Aminocarbonylation Using Electron‐Rich Di‐
tert
‐Butyl‐Phosphinoferrocene
Authors: Busacca Carl A. , Eriksson1* Magnus C. , Qu1* Bo , Lee Heewon , Li Zhibin , Senanayake Chris H. 
Published: March 2016

Abstract

The direct palladium‐catalyzed carbonylation of aryl halides in the presence of alcohols or amines is an efficient way to synthesize esters and amides, respectively. The synthesis of esters is relatively well precedented, whereas the amino carbonylation, which is of great importance for the synthesis of pharmaceuticals, remains a bigger challenge. We demonstrated the amino carbonylation of hetero aryl bromides and iodides using the electron‐rich ligand di‐
tert
‐butyl‐phosphinoferrocene. To our knowledge, this is the first example of gram scale aminocarbonylation that employs base hydrolysis of an imide by‐product to increase the isolated yield.
Preparation of (
S
)‐
tert
‐
ButylPyOx
and Palladium‐Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids
Authors: Holder Jeffrey C. , Shockley Samantha E. , Wiesenfeldt Mario P. , Shimizu Hideki , Stoltz* Brian M. 
Published: March 2016

Abstract

This article reports the palladium‐catalyzed asymmetric conjugate addition of arylboronic acids to cyclic, β,β‐disubstituted enones utilizing (
S
)‐
tert‐
ButylPyOx as the chiral ligand. This robust reaction does not require an inert atmosphere, is highly tolerant of water, and provides cyclic ketones bearing β‐benzylic quaternary stereocenters in high yields and enantioselectivities. In our initial experiments, (
S
)‐
tert‐
ButylPyOx was synthesized by methanolysis of 2‐cyanopyridine, and subsequent acid‐catalyzed cyclization with (
S
)
‐tert‐
leucinol to afford the (
S
)‐
tert‐
ButylPyOx ligand. We found the yields of this reaction sequence to be highly variable, and the purification by silica gel chromatography to be tedious due to the presence of numerous impurities.
One‐Pot Hydrozirconation/Copper‐Catalyzed Conjugate Addition of Alkylzirconocenes to Enones
Authors: Arnold David , Krainz Tanja , Wipf* Peter 
Published: March 2016

Abstract
This article discusses about copper‐catalyzed conjugate Michael reaction and related additions of alkylzirconocenes to α,β‐unsaturated carbonyl compounds which have emerged as synthetically useful C‐C bond forming processes. These reactions are tolerant of cyclic and acyclic alkenes, as well as silyl ether, silyl ester and acetal functionalities. A variety of enones have also been successfully employed, including cyclic, acyclic, sterically hindered and chiral substrates.The procedure exemplifies the utility and scalability of one‐pot hydrozirconation.
Polytropic index of magnetosheath ions based on homogeneous MHD Bernoulli Integral
Authors: Pang Xuexia , Cao Jinbin , Ma Yuduan 
Published: March 2016

AbstractThis paper uses Cluster data during the period from 2001 to 2010 to study the polytropic processes of magnetosheath ions. Utilizing the method of homogeneous magnetohydrodynamic (MHD) Bernoulli integral (MBI), we first identify streamflow tubes, then use the constant of polytropic relation to guarantee that the streamflow tube experiences an unchanged polytropic process, and finally determine the polytropic index of ions in these streamflow tubes. The statistical results show that the magnetosheath is a complicated system in which the polytropic index of ions ranges from −2 to 3. The polytropic index distribution of ions is dependent on the electromagnetic energy flux perpendicular to the streamline. The median polytropic index of ions in the magnetosheath is 0.960, 0.965, and 0.974 for perpendicular electromagnetic energy ratio δE × B < 5%, δE × B < 3%, and δE × B < 1%, respectively. There are two basic polytropic processes in the magnetosheath: the dominant isothermal process and the isobaric process. When there is no exchange of electromagnetic energy between neighboring streamflow tubes, the magnetosheath ions are isothermal. However, when the perpendicular electromagnetic energy ratio increases, the isobaric polytropic process starts to emerge. The magnetosheath ion flows are highly localized because most streamflow tubes experiencing same polytropic processes last less than 60 s. Thus, the polytropic index of magnetosheath ion flows is highly variable.
Graben formation and dike arrest during the 2009 Harrat Lunayyir dike intrusion in Saudi Arabia: Insights from InSAR, stress calculations and analog experiments
Authors: Xu Wenbin , Jónsson Sigurjón , Corbi Fabio , Rivalta Eleonora 
Published: March 2016

AbstractDetailed spatial and temporal accounts of propagating dikes from crustal deformation data, including their interplay with faulting, are rare, leaving many questions about how this interplay affects graben formation and the arrest of dikes unanswered. Here we use interferometric synthetic aperture radar (InSAR) observations, stress calculations, and analog experiments to investigate the interaction between an intruding dike and normal faulting during the 2009 Harrat Lunayyir dike intrusion in western Saudi Arabia. We generated five displacement maps from InSAR data to unravel the temporal evolution of deformation covering the majority of the intrusion. We find that the observed surface displacements can be modeled by a ~2 m thick dike with an upper tip ~2 km below the surface on 16 May 2009, 4 weeks after the onset of seismic unrest. In the following three days, the dike propagated to within ~1 km of the surface with graben‐bounding normal faulting dominating the near‐field deformation. The volume of the dike doubled between mid‐May and mid‐June. We carried out analog experiments that indicate that the wedge‐shaped graben grew outward with the faulting style changing progressively from normal faulting to oblique. Coulomb failure stress change calculations show that the intruding dike caused two zones of shallow horizontal tension on both sides of the dike, producing two zones of fissuring and normal faulting at the surface. In return, the faulting provoked compression around the upper tip of the dike, holding back its vertical propagation.
“Ductile to brittle” transition in thermally stable antigorite gouge at mantle pressures
Authors: Proctor Brooks , Hirth Greg 
Published: March 2016

AbstractGeneral shear experiments on antigorite‐rich serpentinite show a transition from ductile (distributed) to brittle (localized) deformation with increasing temperature from 300°C to 500°C at confining pressures from 1 to 2 GPa. The coefficient of friction associated with slip along fractures decreases from 0.23 to 0.07 with an increase in temperature from 300°C to 500°C. Velocity stepping experiments exhibit a positive rate dependence, as parameterized by a‐b values, that decrease modestly with increasing temperature from ~0.015 at 300°C to ~0.01 at 500°C. Fractures contain fine‐grained foliated antigorite, and there is no evidence of dehydration. All samples have a moderate foliation and show microstructural evidence for both plastic and brittle deformation mechanisms. Under certain conditions the transition to brittle deformation, at high pressures and temperatures in antigorite, might generate earthquakes, which could explain the occurrence of some intermediate‐depth seismicity within subduction zones in serpentinized regions that are too cold to induce dehydration.
Variability of nonlinear internal waves in the South China Sea affected by the Kuroshio and mesoscale eddies
Authors: Li Qiang , Wang Bing , Chen Xu , Chen Xueen , Park Jae‐Hun 
Published: March 2016

AbstractLong‐term observations of nonlinear internal waves in the South China Sea reveal seasonal to interannual variability. During two selected segments of inverted echo sounder observations, tidal forcing in Luzon Strait is almost identical, but the observed amplitudes of nonlinear internal waves in the South China Sea are very different. The effects of the Kuroshio and mesoscale eddies, reproduced by HYbrid Cooridnate Ocean Model (HYCOM) reanalysis simulation, are then investigated. The Kuroshio can enhance the zonal tilt of the thermocline and induce intruding flow in Luzon Strait. During the two selected segments, different thermocline slopes did not significantly change the internal tide generation, but the intruding flow may result in a 11% difference in the amplitude of generated M2 internal tides. During the two selected segments, mesoscale eddies appeared on the path of internal wave propagation, a cold eddy in one case and a warm one in the other. The eddies changed local stratification and induced additional background currents, thus affecting the nonlinear evolution of internal tides. In addition, wave front steering due to the mesoscale eddies dramatically affected the observed amplitude changes of the nonlinear internal waves: the edge, rather than the center, of the nonlinear internal wave front passed through the observational stations, resulting in reduced amplitude in the observations.
Time scales in Galveston Bay: An unsteady estuary
Authors: Rayson Matthew D. , Gross Edward S. , Hetland Robert D. , Fringer Oliver B. 
Published: March 2016

AbstractEstuarine time scales including the turnover, particle e‐folding time, the age (calculated with a passive tracer), and residence time (calculated with Lagrangian particles) were computed using a three‐dimensional hydrodynamic model of Galveston Bay, a low‐flow, partially stratified estuary. Time scales were computed during a time period when river flow varied by several orders of magnitude and all time scales therefore exhibited significant temporal variability because of the unsteadiness of the system. The spatial distributions of age and residence time were qualitatively similar and increased from 15 days in a shipping channel to >45 days in the upper estuary. Volume‐averaged age and residence time decreased during high‐flow conditions. Bulk time scales, including the freshwater and salinity turnover times, were far more variable due to the changing river discharge and salt flux through the estuary mouth. A criterion for calculating a suitable averaging time is discussed to satisfy a steady state assumption and to estimate a more representative bulk time scale. When scaled with a freshwater advective time, all time scales were approximately equal to the advective time scale during high‐flow conditions and many times higher during low‐flow conditions. The mean age, Lagrangian residence, and flushing times exhibited a relationship that was weakly dependent on the freshwater advective time scale demonstrating predictability even in an unsteady, realistic estuary.
Comparison of soil moisture in GLDAS model simulations and in situ observations over the Tibetan Plateau
Authors: Bi Haiyun , Ma Jianwen , Zheng Wenjun , Zeng Jiangyuan 
Published: March 2016

AbstractSoil moisture is a key state variable in many hydrological processes. The Global Land Data Assimilation System (GLDAS) can produce global and continuous soil moisture data sets which have been used in many applications. In this study, simulated soil moisture from four land surface models (LSM) (Mosaic, Noah, Community Land Model, and Variable Infiltration Capacity) in GLDAS‐1 and the more recent GLDAS‐2 were evaluated against in situ soil moisture measurements collected from two soil moisture networks located on the Tibetan Plateau at different soil depths. The two networks provide a representation of different climates and land surface conditions on the Tibetan Plateau which can make the evaluation results more robust and reliable. The results show that all the LSMs can well capture the temporal variation of observed soil moisture with the correlation coefficients mostly being above 0.5. However, they all display biases with the surface soil moisture being systematically underestimated in both of two network regions, and the Mosaic model always shows the largest bias that even reaches 0.192 m3/m3. The causes of the biases were investigated in detail, and we found that the biases may mainly be caused by the soil stratification phenomenon over the Tibetan Plateau. Moreover, errors in model parameters, especially the soil properties data, deficiencies in model structures, and mismatch of the spatial scale and soil depth between LSM simulations and in situ measurements may contribute to the biases as well. Additionally, it was found that GLDAS‐2 nearly does not show superior performance than GLDAS‐1 over the Tibetan Plateau.