bluuebunny/crossref_metadata_2025 huggingface dataset:
A longitudinal examination of psychosocial impairment across the anxiety disorders
Authors: Naragon-Gainey K. , Gallagher M. W. , Brown T. A.
Published: August 2013

Background

Anxiety disorders are highly prevalent disorders associated with substantial psychosocial impairment, but few studies have examined impairment within specific anxiety disorders. Furthermore, it is unclear how change in different types of anxiety has an impact on change in impairment, particularly given high rates of co-morbidity. The current study assessed the temporal associations of impairment and symptoms of three common anxiety disorders in a large, diagnostically heterogeneous clinical sample.

Method

Data were collected from 606 treatment-seeking individuals at an anxiety clinic, most of whom subsequently enrolled in cognitive-behavioral therapy. Symptoms of panic, social anxiety and generalized anxiety disorder (GAD), as well as levels of impairment, were assessed three times over 2 years. In addition to examining levels of impairment across diagnostic groups, latent growth modeling was used to evaluate the longitudinal associations of anxiety symptoms and impairment.

Results

Those with a principal diagnosis of GAD reported higher levels of impairment in some domains at baseline; however, at follow-up assessments individuals with social anxiety disorder reported greater impairment than those with panic disorder. Anxiety symptoms and impairment both declined over time. Change in all three anxiety symptoms was closely associated with change in impairment, but only GAD remained a significant (positive) predictor of change in impairment after accounting for co-morbidity.

Conclusions

Impairment and all three anxiety disorders were closely associated, both cross-sectionally and longitudinally. Because change in GAD was most specifically related to change in impairment, treatment for those with multiple anxiety disorders could focus on treating GAD symptoms first or treating transdiagnostic processes.
Endothelial dysfunction is associated with a greater depressive symptom score in a general elderly population: the Hoorn Study
Authors: van Sloten T. T. , Schram M. T. , Adriaanse M. C. , Dekker J. M. , Nijpels G. , Teerlink T. , Scheffer P. G. , Pouwer F. , Schalkwijk C. G. , Stehouwer C. D. A. , Henry R. M. A.
Published: August 2013

Background

Endothelial dysfunction (ED), low-grade inflammation (LGI) and oxidative stress (OxS) may be involved in the pathobiology of depression. Previous studies on the association of these processes in depression have yielded contradictory results. We therefore investigated comprehensively, in a population-based cohort study, the association between ED, LGI and OxS on the one hand and depressive symptoms on the other.

Method

We used data from the Hoorn Study and determined biomarkers of ED [flow-mediated dilatation (FMD), von Willebrand factor, soluble intercellular adhesion molecule 1 (sICAM-1), soluble vascular cell adhesion molecule 1, soluble thrombomodulin and soluble endothelial selectin], LGI [C-reactive protein, tumour necrosis factor-α, interleukin 6, interleukin 8, serum amyloid A, myeloperoxidase (MPO) and sICAM-1] and OxS (oxidized low density lipoprotein and MPO). Depressive symptoms were quantified by the Center for Epidemiologic Studies Depression Scale (CES-D) questionnaire (n = 493; age 68 years; 49.9% female). Regression analyses were performed with the use of biomarker Z scores. Adjustments were made for age, sex and glucose metabolism status (cohort stratification variables) and prior cardiovascular disease, hypertension, waist-to-hip ratio, cholesterol levels, education level, physical activity, dietary habits, and the use of antihypertensive and/or lipid-lowering medication and/or metformin (potential confounders).

Results

After adjustment for age, sex and glucose metabolism status, one standard deviation increase in the ED Z score was associated with a 1.9 [95% confidence interval (CI) 0.7–3.1] higher CES-D score. Additional adjustments did not materially change this result. LGI and OxS were not associated with the CES-D score.

Conclusions

ED, as quantified by an array of circulating biomarkers and FMD, was independently associated with depressive symptoms. This study supports the hypothesis that ED plays an important role in the pathobiology of depression.
COMMENTS ON “ORDERING PROPERTIES OF ORDER STATISTICS FROM HETEROGENEOUS POPULATIONS: A REVIEW WITH AN EMPHASIS ON SOME RECENT DEVELOPMENTS”
Authors: Xu Maochao
Published: August 2013

Professors Balakrishnan and Zhao have written an excellent survey on the recent developments of stochastic comparisons of order statistics, which cover almost every aspect of ordering properties of order statistics from both continuous and discrete heterogeneous populations. My discussion will be limited to the skewness of order statistics and order statistics from heterogeneous populations with different shape parameters.
COMMENTS ON: ORDERING PROPERTIES OF ORDER STATISTICS FROM HETEROGENEOUS POPULATIONS: A REVIEW WITH AN EMPHASIS ON SOME RECENT DEVELOPMENTS BY N. BALAKRISHNAN AND P. ZHAO
Authors: Khaledi Baha-Eldin
Published: August 2013

I thank the authors for providing another excellent review on stochastic comparisons of order statistics after the review paper written by Kochar and Xu (2007).
AUTHORS' REJOINDER
Authors: Balakrishnan N. , Zhao Peng
Published: August 2013

First of all, we express our sincere thanks to all the discussants for their valuable comments and suggestions as well as for their own significant contributions to the area of order statistics in general, and to the topic of stochastic comparison in particular. We shall now provide our response to the comments and suggestions of all the discussants.
Glottal replacement of /t/ in two British capitals: Effects of word frequency and morphological compositionality
Authors: Schleef Erik
Published: August 2013

This study examines the internal and external constraints on glottal replacement of /t/ among adolescents in London and Edinburgh. Results show that phonological and stylistic constraints play an important role in determining the realizational variation of /t/, as many similar studies have shown. However, there is also clear evidence that our understanding of this phenomenon has been restricted by the limited set of factors that have been investigated previously, as results show that this feature is also constrained by word frequency and morphophonological factors. These findings raise important questions concerning the role of morphological compositionality in language change and the nature of lexical diffusion.
Some Remarks on the Alogi
Authors: Fisher George Park
Published: August 2013

Of late the Alogi (so-called) have been the subject of renewed discussion in Germany. The topic is handled by Dr. A. Harnack in his able and elaborate article on “Monarchianism” in Herzogand Plitt's Encyclopædia (vol. x.), and in his “Dogmengeschichte” (second edition, 1888). It is considered at length in the first half of the first volume of Zahn's “History of the New Testament Canon” (1888). This last publication has called out a polemical review from Harnack, in which the Alogi forms one of the prominent themes. In Zahn's brief pamphlet in reply to Harnack, however, this particular topic is not taken up. The subject, as all are aware, is interesting as a branch of the history of Christology in the second century. It is especially important now for its connection with the debate respecting the authorship of the Fourth Gospel.
The Camisard Uprising of the French Protestants
Authors: Baird Henry Martyn
Published: August 2013

The movement known as the War of the Camisards is an episode of the history of Protestantism in France which, though rarely studied in detail and perhaps but partially understood, was not devoid of significance.
Parochial Libraries in the Colonial Period
Authors: Hurst John Fletcher
Published: August 2013

The Protestant colonists who first came to this continent possessed strong literary tastes. The Dutch were at first controlled largely by the purely commercial spirit, but in a short time a literary tendency developed itself decidedly among them, which was strengthened by a close communication with such literary centres in Holland as Leyden and other seats of learning. No portion of our colonists placed stronger emphasis on the requirements for a learned clergy than the Dutch. The Swedes, for the short time that they held a secure footing on the banks of the Delaware, gave most valuable literary treatment to their colonial home. Luther's Catechism was translated into the Virginian-Indian language, printed in Stockholm in 1696, and sent out under the patronage of King Carl XL, to do missionary work among the savages. Svedberg wrote “America Illuminata,” for the purpose of acquainting his countrymen in Sweden with the New World. Campanius and Acrelius wrote large and full descriptive works, which, for minute treatment, were not surpassed by any writers in the entire colonial period.
The Anabaptists of the Sixteenth Century
Authors: Burrage Henry Sweetser
Published: August 2013

New methods of historical study are securing important results. The demand now is not only that those who write history shall go back to the sources, but that by a thorough examination of the materials which the sources furnish, and by the employment of sound canons of criticism, the facts, so far as possible, shall be obtained. Because of this demand not a little of what has hitherto been regarded as veritable history has been discovered to be untenable and misleading. In no field of historic research are these results more conspicuous than in that which has been traversed in recent years by those who have directed their attention to the history of the Anabaptists of the sixteenth century.
The Vicissitudes of the Doctrine of the Lord's Supper in the English Church: A Study in Dogmatic History
Authors: Richard James William
Published: August 2013

When in the year 1534 Clement VII. decided against Henry VIII., King of England, in the matter of his divorce with Catharine of Aragon, and the spiritual corporations had resolved that the Roman pontiff had no more authority in the kingdom of England than any other foreign bishop, a royal edict abolished the usurped dominion of the Pope. This edict was succeeded in November of the same year by the Act of Supremacy, which reads as follows: “That the Kyng our Soveraign Lorde his heires and successours Kynges of this Realme shal be takyn accepted and reputed the onely supreme heed in erthe of the Churche of England callyd Anglicana Ecclesia.” By this act of Parliament the English Church ceased to be popish, but did not cease to be Romish. The worship was that of Mediæval Catholicism, mainly according to the Sarum Use; the theology was that of Thomas Aquinas, in which Henry himself had been well instructed.
The Bulls Distributing America
Authors: Gordon John
Published: August 2013

When Columbus anchored in the Tagus River, March 5, 1493, he precipitated on Europe one of the most difficult questions with which the mind of man has ever grappled. It was this: By what title should the New World be held ? The Catholic sovereigns Ferdinand and Isabella determined to hold what their Admiral had discovered. But the Spanish lawyers found great difficulty in proving their title under the Roman law, which alone would be accepted as conclusive by the other powers, because it did not recognize the right of discovery. The Roman law recognized the acquisition of property through the operation of either the jus gentium or the jus civile? Under the jus gentium, which alone was applicable in this case, property could be acquired: ist, by occupation, occupatio; 2d, by natural increase, as land formed by seas or rivers, accessio; 3d, by transfer, traditio. The only doctrine suitable to the purposes of Spain was that of “occupation,” which some eminent Roman lawyers incorporated not in the jus gentium but in the jus natura, as affirming a natural right.
Holland and Religious Freedom
Authors: Chambers Talbot Wilson
Published: August 2013

Complete religious freedom never existed upon earth until the present century, and even now it is found only in North America and some of the colonial possessions of Great Britain. The ancient world seems never to have formed the conception of such a thing. Religion was always allied with the State. Each people was supposed to have its own gods whom it worshipped in its own way. And rarely did even foreign conquest deprive the subdued people of their religion. Thus Assyria allowed the settlers who took the place of exiled Israel to have a priest of Israel to “teach them the manner of the God of the land.” 2 Kings xvii., 27. And when the Jews were carried off to Babylon, it appears that they were allowed to retain their own religious usages without hindrance. But whenever propagandism was attempted, or any attack made or supposed to be made on the faith or worship of a people, there came at once a violent reaction. Thus the main charge upon which Socrates was condemned at Athens, was that he did not worship the gods that the city worshipped, but introduced new divinities of his own. Imperial Rome rarely disturbed the religion of the nations which one after another submitted to her authority, yet there was a distinction made in regard to the worships introduced into the Eternal City. Some were allowed, others were forbidden. Christianity with its exelusive claims soon came to be numbered among the latter.
Dr. Schaff as a Literary Worker
Authors: Richardson E. C.
Published: August 2013

My acquaintance with Dr. Schaff was not as long as that of some of those who have read papers at this meeting, but it extended over eight years, and was developed under circumstances various enough to give some clear impressions of the scholar, and of the man. I met him at the Hartford Seminary and at Union Seminary, at his own table and at the Century Club, in Washington, in New York, and in London—here, there, and everywhere. I knew him as host and as guest, as junior partner in literary work and in plans for the promotion of theological learning, and as friendly gossip, interested in the shrewd views which he expressed on every topic under the sun, and pleased (not to confess flattered) to surrender to his all-embracing interrogations wahtever was of interest to him.
Life and Work of Bishop Francis Asbury
Authors: Lowrey Asbury
Published: August 2013

Among the creators of the American nation is Bishop Francis Asbury. Not as a discoverer, a military chieftain, a philosopher, a legislator, or diplomatist, but as a purifier of the nation's morals in its germ. While a galaxy of great men like George Washington, John Adams, Thomas Jefferson, Benjamin Franklin, John Jay, and Alex. Hamilton were fighting for liberty, laying the foundation of government and building up a peerless system of free institutions, Asbury was devoting himself assiduously to the culture of the nation's heart. Nor did he do this with towering intellect like that of Jonathan Edwards, or classic writing like that of Timothy Dwight, or flaming oratory like that of George Whitefield, but by simple unsophisticated preaching, prayer, and expostulation throughout the length and breadth of the colonies and infant States.
The Gospel of Peter
Authors: McGiffert Arthur Cushman
Published: August 2013

It is perhaps not unfitting that some notice should be taken in our Society of Church History of what has proved to be one of the most interesting and important literary finds of recent years. I refer to the Greek MS., discovered by U. Bouriant in a tomb at Akhmîm, Egypt, in 1886, and first published in the fall of 1892. The MS. contains, as is well known, brief fragments of an early Christian Gospel and Apocalypse and two more extended fragments of the Book of Enoch. The fragment of the Apocalyse does not contain the name of its author, but toward the close of the Gospel fragment Peter is indicated as the writer of the Gospel in the sentence: “I Simon Peter and Andrew my brother took our nets and went away to the sea.” We have references in early Christian literature to a Gospel and an Apocalypse of Peter, and there can be little doubt that the fragments in question belong to those long-lost works. I shall concern myself to-day only with the Gospel fragment, which has excited chief interest among scholars and has already given rise to an extended literature.
The Contest for Religious Liberty in Massachusetts
Authors: Burrage Henry S.
Published: August 2013

The General Court of Massachusetts, from the settlement of the Colony, in providing for the support of the Christian ministry, followed the ecclesiastical law which had been in force in England long before the Reformation, viz.: that every man should be taxed for this purpose in the town, parish, precinct, or district where he lived, unless specially exempt. In 1638, it was enacted that “every inhabitant who should not voluntarily contribute to all charges, both in Church and Commonwealth proportionately, according to his ability, should be compelled thereto by assessment.”
The Ecclesiastical Situation in New England Prior to the Revolution
Authors: Allen Joseph Henry
Published: August 2013

In reciting the symptoms of popular discontent in Massachusetts at the time of his recall, in 1774, Governor Hutchinson uses these words: “The people had been persuaded that their religion as well as their liberties was in danger. It was immaterial whether they had been deceived or not: the persuasion was the same; and this was what would cause them to go all lengths, and to surmount the greatest difficulties.” (Hist., vol. iii., p. 455.)
The Amsterdam Correspondence
Authors: Corwin Edward T.
Published: August 2013

The worth of contemporary documents for the writing of history needs no discussion. The zeal of Americans in searching out and accumulating such material has steadily increased since the opening of the present century. Historical societies have sprung up representing States or portions of States, groups of States or the nation, particular denominations or the Church at large. Such societies exist for the sake of collecting and preserving contemporary documents, or of securing specially prepared papers to elucidate particular points of history, or to stimulate to greater diligence in the historic field. Thousands of valuable documents have thus been rescued from oblivion or destruction, and many of them published, leading to new investigations, fresh expositions of history, and still further discoveries.
John Eliot, the Puritan Missionary to the Indians
Authors: Byington Ezra Hoyt
Published: August 2013

Special attention has been called recently to the life and work of the Apostle Eliot by the observance of the two hundred and fiftieth anniversary of his first preaching to the Indians. New facts have been brought to light by recent investigations in respect to his life and work. It is quite possible at this time to form a more intelligent idea of his missions, and of their results, than it was even a generation ago. He is no longer regarded as an isolated missionary, a gifted and saintly man who stood quite apart from his environment; and entered upon a work which the men of his time did not appreciate; but rather as one who sought to carry out in definite and practical ways a missionary idea, which the Puritans had long before accepted, and which number of other men among the Colonists were also seeking to carry to successful results.
Wesley as a Churchman
Authors: Faulkner John Alfred
Published: August 2013

The relation of John Wesley and early Methodism to the Church of England is one of the disputed questions of Church History. It has practical interest as well on account of the repeated attempts to induce the Methodists to return to the Church of England on the ground of the alleged unflinching loyalty of Wesley to the Church, and especially on account of his alleged High-Church notions. From documents lately printed some think that the common notion that Wesley maintained strictly evangelical notions after 1738 must be revised. It is therefore of interest to inquire what was Wesley's real attitude toward the Church of his fathers.
Cognitive Therapy for Social Anxiety Disorder: The Impact of the “Self-Focused Attention and Safety Behaviours Experiment” on the Course of Treatment
Authors: Schreiber Franziska , Heimlich Christiane , Schweitzer Clea , Stangier Ulrich
Published: August 2013

Background and Aims: Several studies have shown that cognitive therapy is an effective treatment for social anxiety disorder (SAD). However, it remains unclear which of the complex interventions are associated with an anxiety reduction during the course of treatment. The aim of this study was to examine the impact of the intervention referred to as the “self-focused attention and safety behaviours experiment” on treatment outcome. Method: This study was part of a randomized controlled trial including 16 sessions of either individual cognitive therapy (CT) or interpersonal therapy (IPT) for SAD. Of particular importance, a concomitant time-series analysis was used to investigate the impact of the self-focused attention and safety behaviours experiment on subsequent social anxiety (1, 2, 3, and 4 weeks after the intervention) in 32 patients with SAD, who are receiving cognitive treatment. Results: The results revealed a significant reduction of social anxiety after the self-focused attention and safety behaviours experiment during the subsequent month of treatment. Conclusion: The findings of the current study confirm current cognitive theories of SAD and demonstrate the importance of interventions that target self-focused attention and safety behaviour in cognitive therapy for SAD.
Brain-based individual differences in online L2 grammatical comprehension
Authors: TANNER DARREN , INOUE KAYO , OSTERHOUT LEE
Published: August 2013

Using event-related potentials (ERPs), we investigated the impact of a range of individual difference measures related to L2 learning on proficient L1 Spanish – L2 English bilinguals’ brain responses during L2 morphosyntactic processing. Although grand mean ERP analyses revealed a biphasic N400–P600 response to English subject–verb agreement violations, subsequent analyses showed that participants’ brain responses varied along a continuum between N400- and P600-dominance. To investigate this pattern, we introduce two novel ERP measures that independently quantify relative brain response type and overall magnitude. Multivariate analyses revealed that larger overall brain responses were associated with higher L2 proficiency, while relative brain response type (N400 or P600) was predicted by a coalition of variables, most notably learners’ motivation and age of arrival in an L2 environment. Our findings show that aspects of a learner's background can differentially impact a learner's overall sensitivity to L2 morphosyntax and qualitative use of linguistic cues during processing.
Browsing Alone: The Differential Impact of Internet Platforms on Political Participation
Authors: IKEDA KEN'ICHI , RICHEY SEAN , TERESI HOLLY
Published: August 2013

We research the political impact of how users access the Internet. Recent research suggests that Internet usage may promote political participation. Internet usage is proposed to be beneficial because it increases activity in diverse politicized social networks and through greater access to information. Even though Internet usage may begin as a non-political activity, we outline several reasons to believe that it may spark later political participation. This impact, however, is likely to be non-existent in new forms of Internet browsing such as through mobile phones, where users do less full-scale browsing. The more difficult browsing interface of mobile phones reduces activity in chat rooms and in-depth browsing of online sources of information which promote participation. To test these ideas, we use nationally representative survey data from Japan, a country which has more pronounced usage of mobile phone browsing. Using a Seemingly Unrelated Regression Model, we also show that the chief determinants of using PC's over mobile phones for Internet browsing are age and education. We then show that PC-based Internet activity correlates with increased political participation, but mobile phone usage correlates with less participation.
The Politics of Financial Crisis Response in Japan and the United States
Authors: LIPSCY PHILLIP Y. , TAKINAMI HIROFUMI
Published: August 2013

We examine the politics of financial crisis response in Japan and the United States. Many existing accounts of Japan's ‘lost decade’ of the 1990s have emphasized Japan-specific factors, such as structural problems, policy errors, and political dysfunction. We argue that Japan may have been subject to a form offirst-mover disadvantage. Like innovation in the private sector, developing effective solutions to novel policy problems requires a messy process of discovery, experimentation, and repeated failure. Much as late-industrializing countries adapted the methods and technologies of early developers, second-movers can apply effective policies demonstrated by first-movers in a more targeted, efficient, and rapid manner. We show that the behavior of Japan and the United States during their respective financial crises is broadly consistent with this theory. In addition, policy adoption in the United States most clearly reflected lessons from Japan in areas where the lessons were considered clear and implementation was less politicized.
The responsibility of the scientist
Authors: Herrlich Peter
Published: August 2013

Do scientists bear the responsibility for how their research is used? What can we learn from wartime and more recent examples of how scientists have handled dual‐use problems of research?
Dose Response and Pharmacokinetics of Tofacitinib (CP‐690,550), an Oral Janus Kinase Inhibitor, in the Treatment of Chronic Plaque Psoriasis
Authors: Tan H , Gupta P , Harness J , Wolk R , Chapel S , Menter A , Strober B , Langley RG , Krishnaswami S , Papp KA
Published: August 2013

Longitudinal nonlinear mixed effects modeling was used to characterize the dose–response profile of tofacitinib using data from a placebo‐controlled dose‐ranging study, where tofacitinib 2, 5, and 15 mg twice daily (b.i.d.) were evaluated for plaque psoriasis treatment. Bayesian estimation was applied with prior information derived from the literature: nonclinical and clinical data in psoriasis, as well as other indications. The probability to achieve a certain target effect associated with a given dose was calculated from the posterior samples. On the basis of these probabilities along with safety considerations, tofacitinib 5 and 10 mg b.i.d. were selected for further testing in confirmatory phase III clinical trials. Pharmacokinetics in patients with psoriasis was characterized using a population‐based modeling approach, and body weight was identified as an important covariate. A subgroup analysis suggested reduced efficacy of tofacitinib with increasing body weight; however, it is unclear whether this trend could be explained by systemic exposure alone.

CPT: Pharmacometrics & Systems Pharmacology (2013) 2, e44; doi:10.1038/psp.2013.22; advance online publication 22 May 2013
Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation
Authors: Sa Jeong-Hoon , Kwak Gye-Hoon , Lee Bo Ram , Park Da-Hye , Han Kunwoo , Lee Kun-Hong
Published: August 2013

As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs) and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media.
Thiol‐ene and Thiol‐yne Chemistry in Ideal Network Synthesis
Authors: Cramer Neil B. , Bowman Christopher N.
Published: August 2013

While the thiol‐X family of reactions has great breadth and depth associated with the opportunity to catalyze the reaction of the thiol with a wide variety of substrates, the radical mediated thiol‐ene and thiol‐yne reactions represent the most broadly implemented of the click family of reactions. The thiol‐ene and thiol‐yne reactions have been used most extensively as network forming polymerization reactions; however, they are also ubiquitous in surface modification, polymer side chain modification and numerous small molecule or other functionalization reactions. These reactions are particularly unique in that they are readily and most commonly initiated by exposure to light, though traditional photoinitiators are not required to initiate the reaction. The ability to photoinitiate these reactions makes them distinctive among the click family of reactions in combining the click nature of the reactions with the 4D spatiotemporal control that photoinitiation yields. Further, in polymer network forming reactions, the thiol‐ene reaction is unique in having essentially no oxygen inhibition and in forming a uniform, homogeneous polymer network that exhibits a sharp, distinctive glass transition.
Thiol‐X Chemistries for the Production of Degradable Polymers
Authors: Poetz Katie L. , Durham Olivia Z. , Shipp Devon A.
Published: August 2013

This Chapter reviews the use of thiol‐X chemistries in the synthesis of degradable polymers. In particular, thiol‐ene and thiol‐Michael chemistries have been widely used because of their ability to be high yielding, orthogonal and functional group tolerant. They also exhibit the capacity to be conducted in physiological conditions, thus allowing them to be utilized in vivo. Furthermore, a wide range of thiol‐containing systems, such as cysteine residues in peptides, can be incorporated into the polymer material, thereby providing functionality that may be specifically tailored, e.g. for targeted delivery, degradation, adhesion or cell growth. Degradation of such polymers may be achieved through a number of bond scission processes, often hydrolysis (e.g. of ester linkages) but may also be catalyzed by enzymes. Continued interest in the development of new materials for tissue engineering and the delivery of therapeutics is bound to further the involvement of thiol‐X chemistries, and should see them become mainstays in the production of biomedical devices in the near future.
Thiol–Thiosulfonate Chemistry in Polymer Science: Simple Functionalization of Polymers via Disulfide Linkages
Authors: Roth Peter J. , Theato Patrick
Published: August 2013

Herein we highlight the reaction of thiols with thiosulfonates yielding asymmetric disulfides. The chapter begins with an overview of the synthesis and reactivity of functional thiosulfonates and is followed by a review of polymeric thiosulfonates. We then emphasize the novel use of thiosulfonates as trapping/functionalization agents for macromolecular thiols obtained from parent (co)polymers prepared by reversible addition‐fragmentation chain transfer (RAFT) radical polymerization. We also note how such facile disulfide‐forming chemistries can be readily employed simultaneously with other highly efficient coupling chemistries with an emphasis on the concurrent reaction of activated esters with amines in the presence of thiosulfonates. Finally, we discuss the use of methyl disulfide (SSMe) functional/end‐modified (co)polymers as reagents for the formation of polymeric self‐assembled monolayers (polymer brushes) on metal surfaces such as nanoparticles and quantum dots.
Nucleophilic Thiol‐alkene Michael Addition for the Functionalization of Polymers and for Bioconjugation
Authors: Jones M W , Haddleton D M
Published: August 2013

Thiol‐ene reactions can be efficiently catalysed by appropriate bases and nucleophiles. The most efficient catalysts are usually primary amines or certain phosphines which preclude the need for light and offer an attractive alternative to radical thiol‐ene reactions, which generally use thermal free radical generators such as azo compounds or light. The base catalysed thiol‐ene lends itself to polymer modification reactions and bioconjugation. Perhaps one of the most utilised thiol‐alkene reactions is the Michael addition at maleimides, which has been used effectively for pegylation and bioconjugation at cysteines. This effective reaction is excellent for site‐specific conjugation at either naturally occurring thiols or where the cysteine has been introduced by chemical or biological manipulation. The Michael addition to maleimides has been extended to substitution reactions at dibromo‐ and dithio‐functional maleimides leading to very efficient reactions. Polymer modification via thiol‐ene Michael addition can occur with either thiol or vinyl functional polymers. Polymeric acrylates can be used as effective bioconjugation agents to cysteine, and polymers containing disulphides or free thiols can be readily modified by reaction with acrylates, methacrylates and related small molecules.
Thiol‐ene/yne Chemistry for the Synthesis of Branched and Star‐shaped Macromolecules
Authors: Jennings Abby R. , Son David Y.
Published: August 2013

The advances and discoveries that have been made in the synthesis of dendrimers and other hyper‐branched materials by employing the anionic thiol‐ene or thiol‐Michael reaction, as well as the free‐radical thiol‐ene and thiol‐yne reactions, are discussed. The characterization methods and potential applications of the resulting materials are also mentioned. The initial examples presented involve using the thiol‐Michael reaction for the convergent synthesis of star polymers, divergent synthesis of dendritic molecules, and dendronizing linear polymers. The free‐radical thiol‐ene and free‐ radical thiol‐yne reactions are discussed next, specifically using these “click” reactions for the divergent synthesis of dendritic molecules and for the syntheses of hyperbranched polymers. Finally, examples of using the thiol‐Michael reaction and the free‐radical thiol‐yne reactions in sequence for the preparation of hyper‐branched materials are conveyed.
Dendritic Polymers from Thiol–Yne Reactions
Authors: Barbey Raphael , Perrier Sébastien
Published: August 2013

We review the use of thiol–yne reaction for the design of branched structures, dendrimers and hyperbranched polymers. In addition to its typical ‘click’ chemistry attributes, the advantages of this reaction include the ability to generate almost perfect branching patterns, the possibility to introduce many more functionalities at each generational step and its tolerance towards chemical functionality, allowing the introduction of a wide range of functional groups into the structures.
Thiol‐X Reactions in Tissue Engineering
Authors: Alge Daniel L. , Anseth Kristi S.
Published: August 2013

Thiol‐based click reactions have played a key role in the synthesis of biomaterial scaffolds for regenerative medicine applications. Of particular importance has been their use in creating cell‐laden hydrogel matrices for both fundamental and translational applications. Thiol‐X reactions are often exploited in biological applications as they allow for the facile incorporation of biofunctional components, which has led to many key advancements for the field of tissue engineering. In this chapter, we summarize the important considerations for cytocompatible macromolecular monomer design and subsequent cellular encapsulation in hydrogel formulations. Briefly, we review the main thiol‐X reactions that have been used to synthesize hydrogel cell scaffold systems; provide a generalized protocol for the preparation of cell‐laden hydrogels; present highlights that demonstrate specific advantages of thiol‐X reactions and advances in their application in regenerative medicine research; and conclude with a prospectus on future directions for the field in using thiol‐X chemistries to engineer more advanced hydrogel materials.
Thiol‐ene Radical Coupling: A Powerful Technique for the Synthesis of Polymer Precursors, Block Copolymers and Graft Copolymers
Authors: Boutevin Bernard , Auvergne Remi , David Ghislain
Published: August 2013

This chapter aims to show how reaching functional oligomers and polymers by thiol‐ene radical coupling. According to the vinyl monomers used, different strategies can be adapted in order to reach either monofunctional or telechelic oligomers. For example, combination of thiol‐ene radical coupling onto a functional monomer provides high value oligomers such as silane‐coupling agents for composite materials. This chapter also discusses thiol‐ene radical coupling onto vinyl‐containing polymers, which leads to partial modification of the properties. Finally, we showed how thiol‐ene radical coupling allows for the synthesis of block copolymers such as PMMA‐b‐PDMS‐b‐PMMA.
Hybrids of Synthetic Polymers and Natural Building Blocks Using Thio‐click
Authors: Stenzel Martina H.
Published: August 2013

The ability to form hybrid materials from the combination of synthetic polymeric materials and naturally occurring biopolymers is of great interest for numerous reasons. First, the blending of properties that can be achieved in this manner expands the properties that can be achieved from each family of materials by themselves. Secondly, the use of naturally occurring biopolymers is seen to be advantageous in the advent and development of green chemistry. Finally, the combination of synthetic polymers and biopolymers renders materials that possess both synthetic features and conventional control over the molecular structure along with the activity associated with the particular biopolymer used. Here, broadly we discuss several classes of biopolymers for which it is advantageous to create synthetic polymer–biopolymer conjugates. Glycopolymers and peptides are discussed extensively, and other classes of biopolymers such as proteins and DNA are discussed more briefly. For each broad class of biopolymers the utilization of thiol‐X chemistry to form the synthetic material‐biopolymer conjugates is discussed with extensive discussion of thiol‐ene/yne reactions, thio‐halogeno reactions, and thio‐para fluoro reactions. The approaches necessary for achieving the desired conjugate in high yield are given.
Surface Engineering with Thiol‐click Chemistry
Authors: Hensarling Ryan M. , Patton Derek L.
Published: August 2013

Thiol-click chemistry has emerged as a powerful approach to engineer the chemical composition of surfaces with high efficiency and modularity. This chapter provides a comprehensive review of literature examples employing thiol-based reactions to modify the surfaces of self-assembled monolayers, polymer surfaces, microporous membranes, nano- and microparticles, and biological surfaces. Although all thiol-based transformations are represented, much of the surface modification literature to date has focused on the radical-mediated thiol-ene and thiol-yne reactions and thiol-Michael reactions to fabricate surfaces with complex, but well-defined chemistries. The primary purpose of this chapter is to illustrate the clear potential and broad utility of thiol-click chemistry for surface engineering applications.
Tangling clustering instability for small particles in temperature stratified turbulence
Authors: Elperin T. , Kleeorin N. , Liberman M. , Rogachevskii I.
Published: August 2013

We study tangling clustering instability of inertial particles in a temperature stratified turbulence with small finite correlation time. It is shown that the tangling mechanism in the temperature stratified turbulence strongly increases the degree of compressibility of particle velocity field. This results in the strong decrease of the threshold for the excitation of the tangling clustering instability even for small particles. The tangling clustering instability in the temperature stratified turbulence is essentially different from the inertial clustering instability that occurs in non-stratified isotropic and homogeneous turbulence. While the inertial clustering instability is caused by the centrifugal effect of the turbulent eddies, the mechanism of the tangling clustering instability is related to the temperature fluctuations generated by the tangling of the mean temperature gradient by the velocity fluctuations. Temperature fluctuations produce pressure fluctuations and cause particle accumulations in regions with increased instantaneous pressure. It is shown that the growth rate of the tangling clustering instability is by \documentclass[12pt]{minimal}\begin{document}$\sqrt{\rm Re} \, (\ell _0 / L_T)^2 / (3 {\rm Ma})^4$\end{document} Re (ℓ0/LT)2/(3 Ma )4 times larger than that of the inertial clustering instability, where Re is the Reynolds number, Ma is the Mach number, ℓ0 is the integral turbulence scale, and LT is the characteristic scale of the mean temperature variations. It is found that depending on the parameters of the turbulence and the mean temperature gradient there is a preferential particle size at which the particle clustering due to the tangling clustering instability is more effective. The particle number density inside the cluster after the saturation of this instability can be by several orders of magnitude larger than the mean particle number density. It is also demonstrated that the evaporation of droplets drastically changes the tangling clustering instability, e.g., it increases the instability threshold in the droplet radius. The tangling clustering instability is of a great importance, e.g., in atmospheric turbulence with temperature inversions.
Nonlinear waves and heat transfer in a falling film of condensate
Authors: Aktershev S. P. , Alekseenko S. V.
Published: August 2013

Nonlinear wave formation and heat transfer in wavy condensate film flowing over the isothermal wall are studied numerically. The integral-boundary-layer model, modified with account of the phase transition has been used to describe the wave motion. The nonlinear evolution of both natural and forced two-dimensional waves was investigated, and wave effect on heat transfer in condensate film was determined. Heat transfer enhancement by waves due to the predominant contribution of the thin residual layer between the peaks was demonstrated. It is shown that by applying the superimposed periodic oscillations, one can intensify heat transfer within a certain range of frequencies as compared to the case of naturally occurring waves.
Davey-Stewartson type equations in 4+2 and 3+1 possessing soliton solutions
Authors: Dimakos M. , Fokas A. S.
Published: August 2013

An integrable generalisation of a Davey-Stewartson type system of two equations involving two scalar functions in 4+2, i.e., in four spatial and two temporal dimensions, has been recently derived by one of the authors. Here, we first show that there exists a reduction of this system to a single equation involving a scalar function in 4+2; we will refer to this equation as the 4+2 Davey-Stewartson equation. We then show that it is possible to reduce this equation to an equation in 3+1, which we will refer to as the 3+1 Davey-Stewartson equation. Furthermore, by employing the so-called direct linearising method, we compute 1- and 2-soliton solutions for both the 4+2 and the 3+1 Davey-Stewartson equations.
GaAs pillar array-based light emitting diodes fabricated by metal-assisted chemical etching
Authors: Mohseni Parsian K. , Hyun Kim Seung , Zhao Xiang , Balasundaram Karthik , Dong Kim Jeong , Pan Lei , Rogers John A. , Coleman James J. , Li Xiuling
Published: August 2013

We demonstrate GaAs pillar array-based light emitting diodes (LEDs) with axial p-i-n junctions fabricated using a room-temperature metal-assisted chemical etching (MacEtch) method. Variations in vertical etch rates for all three doping types of GaAs are investigated as a function of etching temperature, oxidant/acid concentration ratio, and dilution of the etching solution. Control over nanopillar morphologies is demonstrated, simply through modification of the etching conditions. Optical emission enhancement from the MacEtched p-i-n GaAs nanopillar LED is observed, relative to the non-etched planar counterpart, through room-temperature photoluminescence and electroluminescence characterization.
High-speed video study of laser-induced forward transfer of silver nano-suspensions
Authors: Mathews S. A. , Auyeung R. C. Y. , Kim H. , Charipar N. A. , Piqué A.
Published: August 2013

High-speed video (100 000 fps) is used to examine the behavior of silver nanoparticle suspensions ejected from a donor substrate during laser-induced forward transfer (LIFT) as a function of viscosity, donor film thickness, and voxel area. Both high-speed video and inspection of the post-transferred material indicate dramatic changes in the behavior of the fluid as the viscosity of the nano-suspensions increases from that of inks (∼0.01 Pa·s) to pastes (>100 Pa·s). Over a specific range of viscosities (90–150 Pa·s) and laser fluences (35–65 mJ/cm2), the ejected voxels precisely reproduce the size and shape of the laser spot. This LIFT regime is known as laser decal transfer or LDT. Analysis of the high-speed video indicates that the speeds of the voxels released by the LDT process do not exceed 1 m/s. Such transfer speeds are at least an order of magnitude lower than those associated with other LIFT processes, thus minimizing voxel deformation during flight and upon impact with the receiving substrate. Variation in the threshold fluence for initiating the LDT process is measured as a function of donor film thickness and transfer spot size. Overall, the congruent nature of the silver nanopaste voxels deposited by LDT is unique among non-contact digital printing techniques given its control of the voxel's size and shape, thus allowing partial parallelization of the direct-write process.
Simulating zonation in geophysical flows by laboratory experiments
Authors: Di Nitto G. , Espa S. , Cenedese A.
Published: August 2013

The laboratory modelling of a rotating turbulent flow subjected to a β-effect by means of laboratory experiments is considered. In particular the focus has been put on the emergence and the evolution of zonal jet-like structures due to the anisotropization of the upscale energy transfer that can be observed in geophysical flows. The experimental setup consists of a rotating tank in which a turbulent flow is reproduced by electromagnetically forcing a shallow layer of saline solution; this model then reproduces the dynamics in the polar regions simulating the so-called γ-plane by the parabolic surface of the rotating fluid. Several experiments have been performed by changing the main external parameters in order to investigate if the setup is suitable for reproducing the basic dynamics associated with a banded configuration analogous to large scale atmospheric and oceanic circulations. Velocity measurements performed by image analysis have allowed characterization of the flow in terms of mean azimuthal velocity, degree of anisotropy, distribution of energy, and characteristic scales. As expected, zonal jets have been found to dominate the dynamics when the β-effect is stronger.