bluuebunny/crossref_metadata_2025 huggingface dataset:
The
Anabasis
and the Ten Thousand, 401–399
BC
Authors: Trundle Matthew
Published: March 2017

In 401
bc
Cyrus attempted to seize the throne of Persia from his older brother, recruiting over 10,000 Greek mercenaries to his army. His forces marched east to Cunaxa, where Cyrus was killed in battle and his native forces routed. The Greeks retired in good order, and, after rejecting a bid to join the king's forces, elected new generals, including Xenophon, who would later write a history of the campaign. After an epic march north, along the Tigris to Armenia and the Black Sea, the Ten Thousand eventually found ships to take them home. Returning to the Aegean in 400, the force initially entered Thracian service before the survivors joined a Spartan campaign to free the cities of Ionia from Persian control. This force was one of the pioneers of a new style of Greek warfare, employing heavy and light infantry in close cooperation.
Carthaginian Offensives in Sicily, 409–307
BC
Authors: Trundle Matthew
Published: March 2017

The struggle for control of Sicily raged between Carthage and Syracuse for much of the fourth century
bc
, the conflict erupting in 409. Dionysius I, tyrant of Syracuse, spent most of his reign in an ultimately futile attempt to eject the Carthaginians from the island, though he did bring large areas of Calabria (in southern Italy) under the control of Syracuse. His death in 368 ushered in several decades of peace, though hostilities broke out again briefly in the 340s. In 316/315 Agathocles secured autocratic power in Syracuse, and in 311 he invaded Carthaginian territory. Syracuse was besieged, and the war ended in a negotiated peace that left Syracuse weakened but still the dominant Greek power on the island.
The Rise of Macedon, 359–336
BC
Authors: Anson Edward
Published: March 2017

Before Philip's accession in 359
bc
, Macedon had been a kingdom whose considerable potential was repeatedly undermined by dynastic squabbling or interventions by neighbors or southern Greek cities. Philip consolidated royal power internally, played his various enemies off against each other, secured control of lucrative mines, created a powerful army, and used diplomacy to further his ambitions. Athenian influence in the north was removed while Philip's authority expanded into central Greece. Eventually Athens and Thebes sank long‐standing suspicions to oppose Philip at Chaeronea, only to be crushed by Macedonian might. Philip was assassinated before he was able to pursue his ambitions against Persia.
The Illyrian Wars, 229–219
BC
Authors: Erdkamp Paul
Published: March 2017

The First Illyrian War began in 229
bc
, following Illyrian aggression and complaints of piracy from Italian merchants. The Illyrians generally avoided pitched battles, but the Romans were successful in taking their fortresses and were able to impose a humiliating peace in 227. The regional influence of the Illyrian Queen Teuta was gradually supplanted by that of Demetrius of Pharos. The Romans continued diplomatic activity in the region as a sign of continuing interest, and several communities placed themselves under Roman protection. Ten years later, however, Demetrius was beginning to threaten these communities and had allied himself with king Antigonus of Macedon. The Second Illyrian War began in 219. Demetrius placed his confidence in the fortresses of Dimale and Pharos, but the former was taken in only seven days. Demetrius was then lured out of Pharos; after the destruction of his forces, he fled to Macedon. The Romans swiftly reestablished their influence in the region.
The Second Punic War, 220–202
BC
Authors: Owens Eddie
Published: March 2017

The Second Punic War saw Rome's very existence challenged by its greatest enemy, the brilliant Carthaginian general Hannibal, who led his army across the Alps to challenge Roman control of Italy. In spite of four great victories, Hannibal could not force the Romans to negotiate. Instead its massive resources enabled Rome to campaign in Spain, the Balkans, and Sicily while denying Hannibal opportunities for further victories. Ultimately Roman determination prevailed and, when Scipio transported a Roman army to North Africa, Hannibal was summoned home after 15 years, where his first defeat ended the struggle.
The First Macedonian War, 215–205
BC
Authors: Erdkamp Paul
Published: March 2017

Philip of Macedon allied himself with Hannibal in 215
bc
. While the latter rampaged through Italy, Philip would seek to overthrow the Roman protectorate of Illyria. While it is doubtful whether Macedonian forces were ever intended to join the Italian campaign, the Roman fleet made sure that Philip's forces were confined to Greece. The Romans allied themselves with the Aetolian League, whose rivals, the Achaean League, joined Philip. A proxy war spread to mainland Greece, and Philip was thus forced to concentrate on a war with several fronts. In 206, the Aetolians, who had borne the brunt of the war, signed a secret peace with Macedon. The Romans tried to reopen the land front but were unwilling to attack the Macedonians directly and peace was soon signed. The Romans, however, continued to resent Philip and the Aetolians.
Philopoemen in the Peloponnese, 221–192
BC
Authors: McKechnie Paul
Published: March 2017

In the Peloponnese in the late third century, the Achaean League was engaged in opposing Sparta's attempts to reassert its authority over its neighbors, especially Megalopolis and Mantinea. Achaean efforts were often commanded by Philopoemen and were frequently supported by the Romans when they happened to have an army in the Balkans.
The Second Macedonian War, 200–197
BC
Authors: Erdkamp Paul
Published: March 2017

After the inconclusive end of the First Macedonian War with Rome, Philip, knowing the Romans resented the peace, began to strengthen his fleet, but after a series of defeats he conceded dominance at sea to his Greek opponents. He turned instead to besiege Abydos, but, just before its capture, a Roman ambassador arrived with an ultimatum that Philip should submit his quarrels to international arbitration. War was declared in summer 200
bc
, but Roman invasions of Macedonia were hampered by logistical problems. In November 198 a conference between the warring parties was held at Nicaea, but both parties desired a decisive engagement. The two armies met by accident at Cynoscephalae in a hard‐fought action that ultimately resulted in a crushing Roman victory. Philip surrendered shortly afterward.
The War against Antiochus
III
, 191–188
BC
Authors: Erdkamp Paul
Published: March 2017

After defeating Macedon, Flamininus announced the freedom of Greece in 196
bc
, and all Roman forces were withdrawn. The Seleucids under Antiochus became a focus for Greek dissatisfaction with Roman dominance but were keen to avoid direct confrontation. When an anti‐Roman faction gained control of Demetrias, the Aetolian League invited Antiochus to guarantee the freedom of Greece and arbitrate in its dispute with Rome. In late 192, the Aetolians massacred a unit of Roman soldiers and the Senate declared war. Antiochus attempted to defend the pass at Thermopylae, but his army disintegrated after the position was turned. Antiochus retreated to Asia, and the focus of the war shifted to naval domination of the Aegean. Rome eventually won the contest, despite the aid given to Antiochus by the fugitive Hannibal. Roman troops were now able to cross into Asia; the Aetolians, isolated from their allies, sued for peace. Antiochus was decisively defeated at Magnesia and forced to renounce all claims west of the Taurus.
The Maccabean War, 167–161
BC
Authors: Whitby Michael
Published: March 2017

In the 160 s
bc,
attempts by the Seleucid king Antiochus IV led to tensions in Judaea between those supporting integration with the Hellenistic world and Jewish traditionalists. The traditionalists were known as the Maccabees, after their leader's nickname (“Hammer”). Until 160 the Maccabees successfully resisted Seleucid attempts to reassert royal authority, being assisted by Seleucid dynastic rivalries, but the death of Judas Maccabaeus brought resistance to an end. Seleucid success was very brief, since fresh dynastic in‐fighting allowed the Jews to reassert their independence.
The Andriscus Uprising and the Achaean War, 149–146
BC
Authors: Erdkamp Paul
Published: March 2017

Following the Roman reorganization of Greece and Macedon in the settlement of 167
bc
, unrest mounted. Around 150
bc
, Andriscus of Adramyttion, claiming to be Philip, son of Perseus, launched a revolt that quickly spread to all four Macedonian republics. The Senate's initial response was feeble, but the subsequent capture of Thessaly prompted the dispatch of a consular army, which routed the Macedonian forces. Andriscus was handed over to the Romans and eventually executed. Meanwhile, the Achaean League, compelled by the Romans to accept Sparta, mobilized and defeated Sparta's army. The Romans tried to settle the dispute with diplomacy, but the league ignored their overtures and was comprehensively defeated. The league was disbanded, Corinth was destroyed as a warning, and Greece and Macedon were turned into provinces.
The Numantine War, 154–133
BC
Authors: Hoyos Dexter
Published: March 2017

The Spanish town of Numantia, stronghold of the Arevaci, was first besieged by the Romans in 153
bc
to limit the growing influence of the tribe. The siege was unsuccessful and peace was renewed. In 143 the Arevaci took up arms against the Lusitanians, and in 141 and 140 the city was again unsuccessfully attacked. Despite these setbacks, the Romans secured a favorable peace. A new Roman commander renewed hostilities in 138, but to little effect. Morale was damaged, and, after more reverses in 137, a Roman general was captured with his entire army. Humiliatingly, the Numantines released their prisoners and concluded peace, prompting an angry Senate to disavow the agreement. In 134 Scipio Aemilianus arrived in Spain with fresh forces and reestablished discipline. A regular siege was begun, and the city was starved into submission after nine months.
The Jugurthine War, 112–105
BC
Authors: Hoyos Dexter
Published: March 2017

In a power struggle, Jugurtha succeeded in reuniting the kingdom of Numidia (northern Algeria), but in 112
bc
he made the mistake of slaughtering the Roman population when he took his rival's capital, Cirta. An outraged Senate sent out Calpurnius Bestia in 111, but he concluded peace so quickly that the Romans suspected bribery. Promised immunity, Jugurtha was summoned to Rome to explain himself, but he made a second mistake in assassinating a cousin resident in the city. He was forced to leave Rome, and in 110 the Senate ordered a second and equally futile invasion. In 109–108 a third campaign was launched by Metellus, who made steady but slow progress; his deputy, Marius, was given command in 107. Relaxing traditional rules on recruitment, Marius overran Numidia, now joined in its resistance by neighboring Mauretania. Following a series of defeats in 106, the Mauretanians betrayed Jugurtha, and hostilities ceased in 105. Jugurtha was taken to Rome and executed, and a new client king was installed on the throne.
The Roman Conquest of Southern Gaul, 125–121BC
Authors: Rawlings Louis
Published: March 2017

The Romans’ expansion in southern Gaul was intended to help its ally Massilia and open a land route to Roman possessions in Spain. In 121bcthe Allobroges were defeated at Vindalium, and a Gallic confederation was routed on the banks of the Isara. Around 118, the Cimbri and Teutones began their great migration, and in 113 they plundered tribes allied with Rome. After defeating the Romans at Noreia, by 110 the Cimbri and Teutones had entered Gaul, requesting leave to settle. They were unsuccessfully attacked again, and by 107 had been joined by Helvetian tribes. While pursuing these, a Roman army was ambushed and ignominiously surrendered at Aginnum. In 105, facing an even larger tribal confederation and suffering from divided command, the Romans were defeated at Arausio, causing panic in Italy. Marius was elected consul in the emergency, but the tribes turned on Spain instead. They marched on Italy in 102, but the Teutones were decisively defeated by Marius’ reformed army at the river Arc. The Cimbri could not be prevented from crossing the Alps, but in 101 they were brought to battle at Vercellae and again wiped out by Marius.
Campaigns against Pirates, 103–67
BC
Authors: Matyszak Philip
Published: March 2017

Rome's military and diplomatic elimination of potential naval rivals, achieved without a corresponding increase in its own sea power, allowed piracy to flourish. Rome's first attempts to suppress piracy in the Illyrian War of 229
bc
suggested that land campaigning against pirates’ bases was a viable strategy, but it brought few results over the following decades. In 102 a poorly resourced and ultimately unsuccessful war was launched against the Cicilian pirates. In 78–74 a second, more serious, campaign was fought against them, but successes were not consolidated and the pirates expanded their operations to Crete. Some attempts were made to clear the island of piracy, but an inconclusive land war was followed by a hasty treaty. The campaign was resumed in 74 but degenerated into a series of sieges. In 67, following further depredations, Pompey was irregularly elected to suppress piracy throughout the Mediterranean. The seas were temporarily swept clear, but piracy was only reduced to tolerable levels, not eliminated.
The Social War, 91–87
BC
Authors: Matyszak Philip
Published: March 2017

The Social War was fought by the Italians not to free themselves from Roman rule but to be fully assimilated into the Roman state with citizen rights. In 91
bc
the Roman tribune Livius Drusus was murdered after attempting to grant Italians citizenship. The communities of central and southern Italy broke out in open revolt, but without the element of surprise. In the beginning of 90 the Romans lost several fortresses to treachery, but, though the Marsi ambushed and killed a consul, they could not exploit their success. The Samnites, meanwhile, attempted to destroy the Latin colonies that encircled them, but a stalemate soon ensued. In 89, fearing the spread of the revolt, the Romans offered to grant citizenship to all who wanted it, effectively removing the motive for the rebellion. Asculum continued to resist, but, after beating off several attempts to invest the town, its commander despaired of victory and committed suicide. The Marsi fought a final battle near the Fucine Lake, killing another consul, but Roman concessions ultimately extinguished their resistance. In the south, Nola held out until the embers of the Social War were subsumed by a new conflict between Sulla and Marius.
The Mithridatic Wars, 89–66
BC
Authors: Matyszak Philip
Published: March 2017

After Mithridates, king of Pontus, intervened in Cappadocia, the Bithynians and Cappadocians appealed to the Senate. In 89
bc
the Senate's representative was persuaded by Nicomedes of Bithynia to provoke a war, but the combined Roman and Bithynian forces were defeated. Disaffected Greek states flocked to Mithridates. In the campaigns of the First Mithridatic War, the Romans, led by the renegade general Sulla, drove the Pontic forces out of Greece. A brief peace was concluded in 85, and Sulla returned to Rome to face his enemies. War again flared up in 83 but ended inconclusively after a Roman defeat, Sulla ordering his lieutenant to withdraw. In 73 Nicomedes died, supposedly leaving his kingdom to Rome. Mithridates launched a preemptive invasion, and hostilities resumed. Lucullus eventually succeeded in driving Mithridates into Armenia, but mutinies prevent him from finishing the war. Pompey assumed command in 66 and succeeded in outmaneuvering his opponent, destroying his army at the battle of Dasteria. Pontus was annexed, and, though Mithridates fled to the Crimea, he committed suicide following a coup.
Marius versus Sulla, 83–82
BC
Authors: Matyszak Philip
Published: March 2017

After ending the First Mithridatic War, Sulla returned to Italy in 83
bc
to challenge his opponents, now led by the son of his old rival Marius. The Marians had allied themselves with those Italians who had remained in arms after the end of the Social War and were encamped at the base of Mount Tifana, near Capua. Sulla attacked them in camp and routed their forces. The following year Marian forces in the south attacked Sulla, believing his army to be exhausted, but were again decisively routed. A second Sullan army commanded by Metellus eventually defeated the Marians in the north. Sulla settled down to besiege Marius in Praeneste. The last opponents in the field were the Samnites, still in arms following the Social War, who threatened Rome in an attempt to draw Sulla out before his forces could be united. Sulla arrived at Rome by a forced march, his forces winning a hard victory at the Colline Gate. Praeneste surrendered on news of the defeat and Marius committed suicide.
The Second Triumvirate, 43–31
BC
Authors: Matthews Stephen
Published: March 2017

After months of jockeying for advantage, Caesar's assassination produced a formal agreement between his heir (the young Octavian) and two of his experienced lieutenants (Antony and Lepidus) to punish the “liberators” and share authority in the Roman world. Revenge was soon secured, but this left the triumvirs eyeing each other's power. In the east, Antony was defeated by the Parthians, while his attachment to Cleopatra caused scandal. In the west, Octavian's lieutenants, especially Marcus Agrippa, gradually overcame challenges on land and sea until Antony was maneuvered into a conflict in which his declining resources were overcome.
German Campaigns, 55
BC–AD
16
Authors: Campbell Brian
Published: March 2017

Since Caesar's conquest of Gaul, the Romans had come into contact with German raiding parties from across the Rhine. In 17
bc
the Romans suffered an embarrassing defeat, and from 16 to 13
bc
Augustus stationed himself in Gaul, supervising preparations for a major campaign. The invasion was launched in 12
bc
with naval support and advanced as far as the Weser in 11
bc
, but it was forced to retreat soon after. In 9
bc
the Romans penetrated to the Elbe, and preparations were made to make the Roman occupation permanent. By
ad
6, the pacification of Germany between the Rhine and Elbe was so advanced that forces could be removed for a planned invasion of Bohemia. In 9, however, a field army under Publius Quinctilius Varus was wiped out and all Roman garrisons in northern Germany were overrun. The defeat caused a shift in policy, and Augustus decided to settle for control of the Rhine and its environs. Campaigning to restore the situation followed, including incursions across the Rhine in 14, 15, and 16. Feeling Roman prestige had been restored, the new emperor Tiberius ended these costly operations, and the Roman frontier settled on the Rhine.
The Year of the Four Emperors, 69
Authors: Campbell Brian
Published: March 2017

The Jewish revolt of 66 was partly nationalistic and partly inspired by religious feeling, exacerbated by the actions of the Romans. After the first attempt to suppress the revolt failed, the emperor Nero appointed Flavius Vespasianus (the future emperor Vespasian) to a special command. The conquest of Galilee began with the siege of Jotapata, commanded by Josephus, the future historian of the conflict. After Jotapata fell, Josephus chose to collaborate. The advance of the Romans precipitated the overthrow of moderate influences in Jerusalem, but Rome was itself convulsed by civil war, and the campaign languished for much of 69. Vespasian was himself acclaimed emperor in July, and in 70 he resumed the war under the command of his son, Titus. Jerusalem was captured after a brief but bloody siege, and the temple was destroyed. Mopping‐up operations followed, including the siege of Masada, which was finally stormed in 74.
Trajan's Parthian War, 113–117
Authors: Roth Jonathan P.
Published: March 2017

In 114, Trajan reduced the kingdom of Armenia to a province. Chronological confusion in our sources makes it difficult to reconstruct the subsequent campaign; Trajan may have spent the following year pacifying Armenia or moved into eastern Mesopotamia. In 116 a fresh campaign seems to have been launched across the Euphrates. Adiabene was subjugated, and the Romans swung south, capturing the Parthian capital (Ctesiphon) and reaching the Persian Gulf. The Parthians recaptured territory behind the advance but were caught by detached Roman forces. When the Romans finally regrouped, the Parthians were defeated near Ctesiphon, and Trajan installed a puppet king. Hatra was unsuccessfully besieged, probably in 116. The Jews of Africa revolted between 115 and 117, requiring the diversion of major forces. Trajan left for Rome in 117, leaving Hadrian in command in the east, but died on the journey. Hadrian subsequently abandoned many of Trajan's conquests.
Lucius Verus and the East, 161–165
Authors: Roth Jonathan P.
Published: March 2017

In 161 or 162 (the chronology of this campaign is uncertain), the Parthians attempted to install a new king in Armenia. Local Roman intervened but were defeated, and the eastern provinces overrun. Forces were taken from the German frontier, given competent generals, and placed by the emperor Marcus Aurelius under the nominal command of his colleague Lucius Verus. In 163 the Romans took Armenia and made preparations to invade Parthia. The Romans entered Mesopotamia in 165, taking cities including Nisibis and Dura‐Europos, which they retained following the peace. Mesopotamia's largest city, Seleucia, was sacked, and, after the capture of the Parthian capital (Ctesiphon), peace was agreed. The Romans withdrew without adding a new province to the empire but brought back a disastrous plague.
Marcus Aurelius and Europe,

C

. 165–180
Authors: Roth Jonathan P.
Published: March 2017

Little is known about the European campaigns of Marcus Aurelius. In 167, waves of Germanic tribes overran a Pannonian frontier stripped of troops for the Parthian campaign. The barbarians reached northern Italy but withdrew before advancing Roman forces. As further tribes rampaged through the Danubian provinces, a major counteroffensive was launched in 170. After hard fighting, the invaders were driven out by the end of 171. The following year the Romans crossed into German territory; though miracles were occasionally required to extricate the army from its difficulties, by 175 the major tribes were suing for peace. Raiding resumed in 178, but in 179 the major tribal confederacy was comprehensively defeated. Marcus Aurelius died in 180; his son Commodus made peace with the Germans.
The Civil Wars of 193–195
Authors: Roth Jonathan P.
Published: March 2017

Following the assassination of Commodus in 192, the praetorian guard sold the empire to Didius Julianus. Preferring to choose their own candidate, the eastern legions proclaimed Pescennius Niger emperor, while those in Pannonia chose Septimius Severus. Severus marched on Rome, routing Didius, and turned on Niger' forces, besieging Byzantium and driving Niger' field army out of Asia Minor. In 194, Niger was killed and his forces defeated at the battle of Issus. Severus proceeded to invade Parthia. The Parthian campaign was inconclusive, but, despite the death of Niger, Byzantium did not capitulate until 196. Later that year, Clodius Albinus revolted. Severus marched by a circuitous route into Gaul, defeating his opponent at the close‐fought battle of Lugdunum.
The Rise of the Sasanids and the Battle of Hormizdagan, 224
Authors: Hartmann Udo
Published: March 2017

In the early third century, declining Parthian authority was challenged by the Sasanids, subordinate rulers on the Iranian plateau. In 224 Ardashir defeated the last Parthian king and soon imposed his control over the whole kingdom, projecting himself as the favored champion of Zoroastrian religion and embarking on aggressive diplomacy against the Romans.
The Tetrarchy, 284–305
Authors: Hartmann Udo
Published: March 2017

Diocletian was proclaimed emperor by the eastern legions in 284. After winning sole power, he began a fundamental reform of the empire to secure its borders and end the numerous usurpations that had destabilized imperial rule. Accordingly, he divided authority among a college of four rulers. The first major battle of his reign was fought in 285 against Carinus, the son of the previous emperor. Though victorious on the field, Carinus was assassinated shortly afterward. In the winter of 286–287 or 287–288, Carausius set up a secessionist “Britannic empire.” Though initial efforts to remove him were unsuccessful, a series of reverses in 293 led to his assassination and replacement by Allectus. In 296 Britain was invaded and the usurper killed. In the same year, the Persians invaded Armenia. Rome's initial response was a failure, but in 298, while Diocletian put down an Egyptian rebellion, his deputy (Galerius) won a crushing victory in Armenia. Much of the Parthian royal family was captured and the king fled eastward. In 298 peace was concluded and the Tigris made the border between the two empires.
The Rise of Constantine, 306–324
Authors: Humphries Mark
Published: March 2017

The death of the Augustus Constantius I in 306 led to his troops proclaiming his son Constantine as emperor without consulting the other members of the imperial college. In 312 Constantine, seizing a chance to assert sole control in the west, invaded Italy, where he overcame the forces of his rival, Maxentius, ultimately in battle outside Rome, where Constantine attributed victory to the support of the Christian God. Constantine's ambitions now expanded and after 12 years of intermittent tension he overwhelmed his co‐emperor Licinius in engagements at Adrianople and in the Bosporus to establish himself as sole ruler of the Roman world.
Gaul and Spain in the Fifth Century
Authors: Humphries Mark
Published: March 2017

In the fifth century, control in Gaul and Spain was fragmented between competing tribal groups and Roman imperial remnants. In Gaul the Visigoths in the southwest constantly schemed and campaigned to extend their territory toward the Rhone valley, where the Romans were also confronted by the Burgundians. In Spain the Romans had to contain the Sueves, which required Visigothic help, as did their confrontation of Attila. These conflicts in the south helped the rise to power further north of the Franks, who were able to drive the Visigoths into Spain and end all vestiges of Roman control.
A novel mutation in KIF5A in a Malian family with spastic paraplegia and sensory loss
Authors: Guinto Cheick O. , Diarra Salimata , Diallo Salimata , Cissé Lassana , Coulibaly Thomas , Diallo Seybou H. , Taméga Abdoulaye , Chen Ke‐Lian , Schindler Alice B. , Bagayoko Koumba , Simaga Assiatou , Blackstone Craig , Fischbeck Kenneth H. , Landouré Guida
Published: March 2017

Hereditary spastic paraplegias (HSPs) are well‐characterized disorders but rarely reported in Africa. We evaluated a Malian family in which three individuals had HSP and distal muscle atrophy and sensory loss. HSP panel testing identified a novel heterozygous missense mutation in KIF5A (c.1086G>C, p.Lys362Asn) that segregated with the disease (SPG10). Lys362 is highly conserved across species and Lys362Asn is predicted to be damaging. This study shows that HSPs are present in sub‐Saharan Africa, although likely underdiagnosed. Increasing efficiency and decreasing costs of DNA sequencing will make it more feasible to diagnose HSPs in developing countries.
Preparation of Cytocompatible ITO Neuroelectrodes with Enhanced Electrochemical Characteristics Using a Facile Anodic Oxidation Process
Authors: Vallejo‐Giraldo Catalina , Pampaloni Niccolò Paolo , Pallipurath Anuradha R. , Mokarian‐Tabari Parvaneh , O'Connell John , Holmes Justin D. , Trotier Alexandre , Krukiewicz Katarzyna , Orpella‐Aceret Gemma , Pugliese Eugenia , Ballerini Laura , Kilcoyne Michelle , Dowd Eilís , Quinlan Leo R. , Pandit Abhay , Kavanagh Paul , Biggs Manus Jonathan Paul
Published: March 2017

Physicochemical modification of implantable electrode systems is recognized as a viable strategy to enhance tissue/electrode integration and electrode performance in situ. In this work, a bench‐top electrochemical process to formulate anodized indium tin oxide (ITO) films with altered roughness, conducting profiles, and thickness is explored. In addition, the influence of these anodized films on neural cell adhesion, proliferation, and function indicates that anodized ITO film cytocompatibility can be altered by varying the anodization current density. Furthermore, ITO‐anodized films formed with a current density of 0.4 mA cm−2show important primary neural cell survival, modulation of glial scar formation, and promotion of neural network activity.
Multilayered Lipid Membrane Stacks for Biocatalysis Using Membrane Enzymes
Authors: Heath George R. , Li Mengqiu , Rong Honling , Radu Valentin , Frielingsdorf Stefan , Lenz Oliver , Butt Julea N. , Jeuken Lars J. C.
Published: March 2017

Multilayered or stacked lipid membranes are a common principle in biology and have various functional advantages compared to single‐lipid membranes, such as their ability to spatially organize processes, compartmentalize molecules, and greatly increase surface area and hence membrane protein concentration. Here, a supramolecular assembly of a multilayered lipid membrane system is reported in which poly‐l‐lysine electrostatically links negatively charged lipid membranes. When suitable membrane enzymes are incorporated, either an ubiquinol oxidase (cytochrome bo
3 from Escherichia coli) or an oxygen tolerant hydrogenase (the membrane‐bound hydrogenase from Ralstonia eutropha), cyclic voltammetry (CV) reveals a linear increase in biocatalytic activity with each additional membrane layer. Electron transfer between the enzymes and the electrode is mediated by the quinone pool that is present in the lipid phase. Using atomic force microscopy, CV, and fluorescence microscopy it is deduced that quinones are able to diffuse between the stacked lipid membrane layers via defect sites where the lipid membranes are interconnected. This assembly is akin to that of interconnected thylakoid membranes or the folded lamella of mitochondria and has significant potential for mimicry in biotechnology applications such as energy production or biosensing.
High‐Energy‐Density Dielectric Polymer Nanocomposites with Trilayered Architecture
Authors: Liu Feihua , Li Qi , Cui Jin , Li Zeyu , Yang Guang , Liu Yang , Dong Lijie , Xiong Chuanxi , Wang Hong , Wang Qing
Published: March 2017

The development of advanced dielectric materials with high electric energy densities is of crucial importance in modern electronics and electric power systems. Here, a new class of multilayer‐structured polymer nanocomposites with high energy and power densities is presented. The outer layers of the trilayered structure are composed of boron nitride nanosheets dispersed in poly(vinylidene fluoride) (PVDF) matrix to provide high breakdown strength, while PVDF with barium strontium titanate nanowires forms the central layer to offer high dielectric constant of the resulting composites. The influence of the filler contents on the electrical polarization, breakdown strength, and energy density is examined. Simulations are carried out to model the electrical tree formation in the layered nanocomposites and to verify the experimental breakdown results. The trilayered polymer nanocomposite with an optimized filler content displays a discharged energy density of 20.5 J cm−3 at Weibull breakdown strength of 588 MV m−1, which is among the highest discharged energy densities reported so far. Moreover, the nanocomposite exhibits a superior power density of 0.91 MW cm−3, more than nine times that of the commercially available biaxially oriented polypropylene. The findings of this research provide a new design paradigm for high‐performance dielectric polymer nanocomposites.
The Contributions of Polar Nanoregions to the Dielectric and Piezoelectric Responses in Domain‐Engineered Relaxor‐PbTiO3 Crystals
Authors: Li Fei , Zhang Shujun , Xu Zhuo , Chen Long‐Qing
Published: March 2017

The existence of polar nanoregions is the most important characteristic of relaxor‐based ferroelectric materials. Recently, the contributions of polar nanoregions to the shear piezoelectric property of relaxor‐PbTiO3 (PT) crystals are confirmed in a single domain state, accounting for 50%–80% of room temperature values. For electromechanical applications, however, the outstanding longitudinal piezoelectricity in domain‐engineered relaxor‐PT crystals is of the most significance. In this paper, the contributions of polar nanoregions to the longitudinal properties in [001]‐poled Pb(Mg1/3Nb2/3)O3‐0.30PbTiO3 and [110]‐poled Pb(Zn1/3Nb2/3)O3‐0.15PbTiO3 (PZN‐0.15PT) domain‐engineered crystals are studied. Taking the [110]‐poled tetragonal PZN‐0.15PT crystal as an example, phase‐field simulations of the domain structures and the longitudinal dielectric/piezoelectric responses are performed. According to the experimental results and phase‐field simulations, the contributions of polar nanoregions (PNRs) to the longitudinal properties of relaxor‐PT crystals are successfully explained on the mesoscale, where the PNRs behave as “seeds” to facilitate macroscopic polarization rotation and enhance electric‐field‐induced strain. The results reveal the importance of local structures to the macroscopic properties, where a modest structural variation on the nanoscale greatly impacts the macroscopic properties.
Rediscovering the Crystal Chemistry of Borides
Authors: Akopov Georgiy , Yeung Michael T. , Kaner Richard B.
Published: March 2017

For decades, borides have been primarily studied as crystallographic oddities. With such a wide variety of structures (a quick survey of the Inorganic Crystal Structure Database counts 1253 entries for binary boron compounds!), it is surprising that the applications of borides have been quite limited despite a great deal of fundamental research. If anything, the rich crystal chemistry found in borides could well provide the right tool for almost any application. The interplay between metals and the boron results in even more varied material's properties, many of which can be tuned via chemistry. Thus, the aim of this review is to reintroduce to the scientific community the developments in boride crystal chemistry over the past 60 years. We tie structures to material properties, and furthermore, elaborate on convenient synthetic routes toward preparing borides.
Atomimetic Mechanical Structures with Nonlinear Topological Domain Evolution Kinetics
Authors: Frazier Michael J. , Kochmann Dennis M.
Published: March 2017

A mechanical metamaterial, a simple, periodic mechanical structure, is reported, which reproduces the nonlinear dynamic behavior of materials undergoing phase transitions and domain switching at the structural level. Tunable multistability is exploited to produce switching and transition phenomena whose kinetics are governed by the same Allen–Cahn law commonly used to describe material‐level, structural‐transition processes. The reported purely elastic mechanical system displays several key features commonly found in atomic‐ or mesoscale physics of solids. The rotating‐mass network shows qualitatively analogous features as, e.g., ferroic ceramics or phase‐transforming solids, and the discrete governing equation is shown to approach the phase field equation commonly used to simulate the above processes. This offers untapped opportunities for reproducing material‐level, dissipative and diffusive kinetic phenomena at the structural level, which, in turn, invites experimental realization and paves the road for new active, intelligent, or phase‐transforming mechanical metamaterials bringing small‐scale processes to the macroscopically observable scale.
The association of maternal lymphatic markers and critical congenital heart defects in the fetus—A population based case‐control study
Authors: Steurer Martina A. , Norton Mary E. , Baer Rebecca J. , Shaw Gary M. , Keating Sheila , Moon‐Grady Anita J. , Chambers Christina D. , Jelliffe‐Pawlowski Laura L.
Published: March 2017

The objective ot this study was to investigate whether lymphatic markers measured in women during the second trimester are associated with critical congenital heart defects (CCHDs) in offspring. This is a retrospective cohort study of pregnant women who participated in the California Prenatal Screening Program. CCHD data in the offspring was captured by linking birth certificate data with hospital patient discharge records. Second trimester samples were assayed for vascular endothelial growth factor (VEGF), platelet derived growth factor (PDGF) AA/BB, and PDGF AB. Logistic models were used to evaluate the association between lymphatic biomarkers and CCHD. Models were adjusted for other serum biomarkers and maternal characteristics. Results are presented in odds ratios (OR) with 95% confidence intervals (CI). We identified 93 cases with CCHDs and 194 controls without CCHDs. The crude and adjusted OR for log (ln) VEGF was 1.07 (95%CI 0.94–1.22) and 1.08 (95%CI 0.94–1.24), respectively; for ln PDGF AB/BB was 0.93 (95%CI 0.6–1.35) and 0.58 (95%CI 0.32–1.05), respectively. There was a significant association between ln PDFG AA and CCHDs (crude OR 1.83 (95%CI 1.05–3.2); adjusted OR 2.41 (95%CI 1.06–5.44)). Levels of circulating PDGF AA were highest in cases with hypoplastic left heart syndrome (HLHS) (mean 8.78 +/− 1.54 pg/ml). In this study, increased mid‐pregnancy maternal serum levels of PDGF AA were associated with CCHDs in offspring. The highest PDGF AA levels were found in mothers of fetuses with HLHS. These findings may be useful in screening for CCHDs and offer insight into their association with nuchal translucency.
Coherent backscattering in the Fock space of ultracold bosonic atoms
Authors: Schlagheck Peter , Dujardin Julien
Published: March 2017

We present numerical evidence for the occurrence of coherent backscattering in the Fock space of a small disordered Bose‐Hubbard system consisting of four sites and containing five particles. This many‐body interference phenomenon can most conveniently be seen in time evolution processes that start from a Fock state of the Bose‐Hubbard system. It manifests itself in an enhanced detection probability of this initial state as compared to other Fock states with comparable total energy. We argue that coherent backscattering in Fock space can be experimentally measured with ultracold bosonic atoms in optical lattices using state‐of‐the‐art single‐site detection techniques. A synthetic gauge field can be induced in order to break time‐reversal symmetry within the lattice and thereby destroy coherent backscattering. While this many‐body interference effect is most prominently visible in the presence of eigenstate thermalization, we briefly discuss its significance in the opposite regime of many‐body localization.

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A Molecular Circuit Regenerator to Implement Iterative Strand Displacement Operations
Authors: DelRosso Nicole V. , Hews Sarah , Spector Lee , Derr Nathan D.
Published: March 2017

The predictable chemistry of Watson–Crick base‐pairing imparts a unique structural programmability to DNA, enabling the facile design of molecular reactions that perform computations. However, many of the current architectures limit devices to a single operational cycle. Herein, we introduce the design of the “regenerator”, a device based on coupled enthalpic and entropic reactions that permits the regeneration of molecular circuit components.
Enantioselective Formal α‐Methylation and α‐Benzylation of Aldehydes by Means of Photo‐organocatalysis
Authors: Filippini Giacomo , Silvi Mattia , Melchiorre Paolo
Published: March 2017

Detailed herein is the photochemical organocatalytic enantioselective α‐alkylation of aldehydes with (phenylsulfonyl)alkyl iodides. The chemistry relies on the direct photoexcitation of enamines to trigger the formation of reactive carbon‐centered radicals from iodosulfones, while the ground‐state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl and benzyl groups.
Highly Active GaN‐Stabilized Ta3N5 Thin‐Film Photoanode for Solar Water Oxidation
Authors: Zhong Miao , Hisatomi Takashi , Sasaki Yutaka , Suzuki Sayaka , Teshima Katsuya , Nakabayashi Mamiko , Shibata Naoya , Nishiyama Hiroshi , Katayama Masao , Yamada Taro , Domen Kazunari
Published: March 2017

Ta3N5 is a very promising photocatalyst for solar water splitting because of its wide spectrum solar energy utilization up to 600 nm and suitable energy band position straddling the water splitting redox reactions. However, its development has long been impeded by poor compatibility with electrolytes. Herein, we demonstrate a simple sputtering‐nitridation process to fabricate high‐performance Ta3N5 film photoanodes owing to successful synthesis of the vital TaOδ precursors. An effective GaN coating strategy is developed to remarkably stabilize Ta3N5 by forming a crystalline nitride‐on‐nitride structure with an improved nitride/electrolyte interface. A stable, high photocurrent density of 8 mA cm−2 was obtained with a CoPi/GaN/Ta3N5 photoanode at 1.2 VRHE under simulated sunlight, with O2 and H2 generated at a Faraday efficiency of unity over 12 h. Our vapor‐phase deposition method can be used to fabricate high‐performance (oxy)nitrides for practical photoelectrochemical applications.
B(C6F5)3‐Catalyzed Selective Chlorination of Hydrosilanes
Authors: Chulsky Karina , Dobrovetsky Roman
Published: March 2017

The chlorination of Si−H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl2, and CCl4. The catalytic chlorination of silanes often involves the use of expensive transition‐metal catalysts. By a new simple, selective, and highly efficient catalytic metal‐free method for the chlorination of Si−H bonds, mono‐, di‐, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O⋅B(C6F5)3 and HCl with the release of H2 as a by‐product. The hydrides in di‐ and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O⋅B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.
Nonribosomal Peptide Synthesis—Principles and Prospects
Authors: Süssmuth Roderich D. , Mainz Andi
Published: March 2017

Nonribosomal peptide synthetases (NRPSs) are large multienzyme machineries that assemble numerous peptides with large structural and functional diversity. These peptides include more than 20 marketed drugs, such as antibacterials (penicillin, vancomycin), antitumor compounds (bleomycin), and immunosuppressants (cyclosporine). Over the past few decades biochemical and structural biology studies have gained mechanistic insights into the highly complex assembly line of nonribosomal peptides. This Review provides state‐of‐the‐art knowledge on the underlying mechanisms of NRPSs and the variety of their products along with detailed analysis of the challenges for future reprogrammed biosynthesis. Such a reprogramming of NRPSs would immediately spur chances to generate analogues of existing drugs or new compound libraries of otherwise nearly inaccessible compound structures.
Hybrid modification of high‐density polyethylene with hyperbranched polyethylene‐functionalized multiwalled carbon nanotubes and few‐layered graphene
Authors: Lu Tiemei , Ye Huijian , Zheng Aiai , Xu Xilian , Xu Chunfeng , Wang Haiping , Sun Li , Xu Lixin
Published: March 2017

Herein, a facile method has been reported to efficiently prepare debundled multiwalled carbon nanotubes (MWCNT) and few‐layered graphene using a hyperbranched polyethylene (HBPE), and as hybrid fillers, their modification effects on high‐density polyethylene (HDPE) are well demonstrated. Stable dispersions of debundled MWCNT and graphene in chloroform were respectively obtained by sonication using the HBPE as stabilizer, and MWCNT/graphene/HDPE ternary nanocomposites were then fabricated by solution‐assisted premixing and subsequent melt mixing, at a fixed mass ratio of MWCNT/graphene of 3:1 and serially changed filler loadings. It is found that the MWCNT and graphene have good dispersibility in the composites, and as hybrid fillers, they can effectively form composite net‐like structure, which makes them show better modification effects on both the electrically and thermally conductive properties of HDPE, as compared to the single MWCNT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44848.
A 9‐pool metabolic structured kinetic model describing days to seconds dynamics of growth and product formation by Penicillium chrysogenum
Authors: Tang Wenjun , Deshmukh Amit T. , Haringa Cees , Wang Guan , van Gulik Walter , van Winden Wouter , Reuss Matthias , Heijnen Joseph J. , Xia Jianye , Chu Ju , Noorman Henk J.
Published: March 2017

A powerful approach for the optimization of industrial bioprocesses is to perform detailed simulations integrating large‐scale computational fluid dynamics (CFD) and cellular reaction dynamics (CRD). However, complex metabolic kinetic models containing a large number of equations pose formidable challenges in CFD‐CRD coupling and computation time afterward. This necessitates to formulate a relatively simple but yet representative model structure. Such a kinetic model should be able to reproduce metabolic responses for short‐term (mixing time scale of tens of seconds) and long‐term (fed‐batch cultivation of hours/days) dynamics in industrial bioprocesses. In this paper, we used Penicillium chrysogenum as a model system and developed a metabolically structured kinetic model for growth and production. By lumping the most important intracellular metabolites in 5 pools and 4 intracellular enzyme pools, linked by 10 reactions, we succeeded in maintaining the model structure relatively simple, while providing informative insight into the state of the organism. The performance of this 9‐pool model was validated with a periodic glucose feast–famine cycle experiment at the minute time scale. Comparison of this model and a reported black box model for this strain shows the necessity of employing a structured model under feast–famine conditions. This proposed model provides deeper insight into the in vivo kinetics and, most importantly, can be straightforwardly integrated into a computational fluid dynamic framework for simulating complete fermentation performance and cell population dynamics in large scale and small scale fermentors. Biotechnol. Bioeng. 2017;114: 1733–1743. © 2017 Wiley Periodicals, Inc.
Halogenated Briarane Diterpenes with Acetyl Migration from the Gorgonian Coral Junceella fragilis
Authors: Cheng Wei , Li Xiaodan , Yin Fuling , van Ofwegen Leen , Lin Wenhan
Published: March 2017

Chemical examination of the gorgonian coral Junceella fragilis resulted in the isolation of four pairs of acetyl isomers belonging to briarane diterpenoids, including five new compounds. Their structures were determined on the basis of extensive spectroscopic (IR, MS, NMR, and single‐crystal X‐ray diffraction) analysis in association with the chemical conversion. Each pair of isomers featured by dynamical interconversion through as acetyl migration in 1,2‐diol, which was postulated to be generated under the formation of a cyclic orthoacetate intermediate. All compounds exerted the inhibitory activities against the nitric oxide production in RAW264.7 macrophage cells.