Die vorliegende Dissertation beschäftigt sich mit Wachstum und Aufbau von Fluorapatit-Gelatine-Nanokompositaggregaten. Diese Aggregate werden im sogenannten Doppeldiffusionsversuch biomimetisch erzeugt und ihre äußere Form bzw. Formentwicklung lässt sich anhand eines fraktalen Modells bis ins Detail nachvollziehen. Sie zeigen einen komplexen inneren Aufbau, in dem die Makromoleküle der organischen Komponente einerseits im Zentrum jeder Nanoeinheit und andererseits zu Strängen, den sogenannten Fibrillen, zusammengelagert am Aufbau der Kompositaggregate beteiligt sind. Im Fall des Kompositkeims ist die innere Architektur in hoher Detailstufe verstanden, auch wenn -- insbesondere bezüglich der späteren Wachstumsphasen -- eine Reihe ungeklärter Fragestellungen verbleibt. Ein zentrales Ergebnis der vorliegenden Arbeit bildet die Entdeckung eines weiteren Wachstumstypen, der im Vergleich zu den bekannten, fraktalen Kompositaggregaten grundsätzliche Unterschiede bezüglich des inneren und äußeren Aufbaus zeigt. Der Grund für die andersartige Formentwicklung liegt in der Versteifung der organischen Komponente durch eine vorangegangene Einlagerung von Calciumionen, wie sowohl experimentell als auch mit atomistischen Computersimulationen gezeigt werden konnte. Aufgrund der hohen Komplexität des Systems ist es bislang allerdings nicht möglich, lokale Ionen-Konzentrationen und pH-Werte vor bzw. während Nukleation und Wachstum der Kompositaggregate im Doppeldiffusionsversuch zu bestimmen. Deshalb wurde ein Ersatzversuch -- der sehr ähnlich strukturierte Aggregate erzeugt, sich aber mit rechnerischen Methoden analysieren lässt -- entworfen und untersucht. Anhand dieser Ergebnisse konnte erstmals die "Geschichte" von Fluorapatit-Gelatine-Nanokompositaggregaten detailliert nachvollzogen werden. Da über die Rolle der Gelatine beim Wachstum der Kompositaggregate nur wenig bekannt ist, wurde eine Reihe von Versuchen durchgeführt, in denen Gelatinen mit verschiedenen Molekülmassenverteilungen eingesetzt wurden. Es stellte sich heraus, dass für selbstorganisiertes und insbesondere fraktales Wachstum der Kompositaggregate lange, möglichst wenig gestörte Makromoleküle von zentraler Wichtigkeit sind. Um die Funktion der organischen Komponente für das Kompositwachstum näher zu untersuchen, wurden Oberflächen von Kompositkeimen mit rasterkraftmikroskopischen Methoden studiert. Durch Säuberung der Oberflächen konnten Austrittsstellen der organischen Komponente durch die Oberfläche der Kompositkeime identifiziert werden. Damit konnte gezeigt werden, dass die organische Komponente aus dem Inneren des Festkörpers teilweise durch die Oberfläche dringt und somit während des Wachstums weit in das Gel hineinreichen sollte. Für die mesoskopische Strukturbildung der Kompositaggregate spielen intrinsische elektrische Felder eine essenzielle Rolle. Deshalb wurde bislang eine Wirkung externer elektrischer Felder auf das Wachstum der Kompositaggregate vermutet. Im Rahmen der vorliegenden Arbeit wurde herausgearbeitet, dass es zwar zu keiner direkten Beeinflussung kommen kann, jedoch in den elektrodennahen Bereichen des Gels eine Ordnung der organischen Moleküle durch externe elektrische Felder zu erwarten ist. Dies könnte eine Wirkung auf wachsende Kompositaggregate zeigen. Da diese Effekte auch aufgrund der elektrischen Felder um die dipolaren Kompositaggregate zu erwarten sind, könnte eine ähnliche Strukturierung der Gelatine in der Nähe der wachsenden Kompositaggregate stattfinden. Insgesamt wurden in dieser Arbeit eine Reihe grundlegender Beiträge zur Erforschung der biomimetisch erzeugten Fluorapatit-Gelatine-Nanokompositaggregate geleistet. Es konnten neue Erkenntnisse zur inneren und äußeren Architektur der Kompositaggregate, zu Mechanismen der Morphogenese und deren wichtigsten Einflussgrößen sowie zum Verständnis der chemisch-physikalischen Vorgänge auf atomarer Größenskala gewonnen werden. Als besonders fruchtbar erwies sich die Verbindung von Experimenten mit theoretischen Untersuchungen, so dass dieser Weg auch in Zukunft grundlegende Erkenntnisse bei der Erforschung der Biomineralisation verspricht und weiterhin verfolgt werden sollte.

<p><!--[if gte mso 9]><xml> <o:OfficeDocumentSettings> <o:AllowPNG/> </o:OfficeDocumentSettings></xml><![endif]--></p><p><!--[if gte mso 9]><xml> <w:WordDocument> <w:View>Normal</w:View> <w:Zoom>0</w:Zoom> <w:TrackMoves/> <w:TrackFormatting/> <w:DoNotShowRevisions/> <w:DoNotPrintRevisions/> <w:DoNotShowMarkup/> <w:DoNotShowComments/> <w:DoNotShowInsertionsAndDeletions/> <w:DoNotShowPropertyChanges/> <w:HyphenationZone>21</w:HyphenationZone> <w:PunctuationKerning/> <w:ValidateAgainstSchemas/> <w:SaveIfXMLInvalid>false</w:SaveIfXMLInvalid> <w:IgnoreMixedContent>false</w:IgnoreMixedContent> <w:AlwaysShowPlaceholderText>false</w:AlwaysShowPlaceholderText> <w:DoNotPromoteQF/> <w:LidThemeOther>EN-US</w:LidThemeOther> <w:LidThemeAsian>X-NONE</w:LidThemeAsian> <w:LidThemeComplexScript>X-NONE</w:LidThemeComplexScript> <w:Compatibility> <w:BreakWrappedTables/> <w:SnapToGridInCell/> <w:WrapTextWithPunct/> <w:UseAsianBreakRules/> <w:DontGrowAutofit/> <w:SplitPgBreakAndParaMark/> <w:EnableOpenTypeKerning/> <w:DontFlipMirrorIndents/> <w:OverrideTableStyleHps/> </w:Compatibility> <m:mathPr> <m:mathFont m:val="Cambria Math"/> <m:brkBin m:val="before"/> <m:brkBinSub m:val="&#45;-"/> <m:smallFrac m:val="off"/> <m:dispDef/> <m:lMargin m:val="0"/> <m:rMargin m:val="0"/> <m:defJc m:val="centerGroup"/> <m:wrapIndent m:val="1440"/> <m:intLim m:val="subSup"/> <m:naryLim m:val="undOvr"/> </m:mathPr></w:WordDocument></xml><![endif]--></p><p><span id="cke_bm_202S" style="display: none;">&nbsp;</span><span id="cke_bm_207S" style="display: none;">&nbsp;</span><span lang="EN-GB" style="font-size:12.0pt;font-family:&quot;Times New Roman&quot;,&quot;serif&quot;;mso-fareast-font-family:&quot;Droid Sans Fallback&quot;;color:black;mso-font-kerning:.5pt;mso-ansi-language:EN-GB;mso-fareast-language:ZH-CN;mso-bidi-language:HI"><span id="cke_bm_207E" style="display: none;">&nbsp;</span><span id="cke_bm_202E" style="display: none;"> </span></span><!--[if gte mso 10]><style> /* Style Definitions */ table.MsoNormalTable{mso-style-name:"Table Normal";mso-tstyle-rowband-size:0;mso-tstyle-colband-size:0;mso-style-noshow:yes;mso-style-priority:99;mso-style-parent:"";mso-padding-alt:0cm 5.4pt 0cm 5.4pt;mso-para-margin-top:0cm;mso-para-margin-right:0cm;mso-para-margin-bottom:8.0pt;mso-para-margin-left:0cm;line-height:107%;mso-pagination:widow-orphan;font-size:11.0pt;font-family:"Calibri","sans-serif";mso-ascii-font-family:Calibri;mso-ascii-theme-font:minor-latin;mso-hansi-font-family:Calibri;mso-hansi-theme-font:minor-latin;mso-ansi-language:EN-US;mso-fareast-language:EN-US;}</style><![endif]--></p><p><!--[if gte mso 9]><xml> <o:OfficeDocumentSettings> <o:AllowPNG/> </o:OfficeDocumentSettings></xml><![endif]--><!--[if gte mso 9]><xml> <w:WordDocument> <w:View>Normal</w:View> <w:Zoom>0</w:Zoom> <w:TrackMoves/> <w:TrackFormatting/> <w:DoNotShowRevisions/> <w:DoNotPrintRevisions/> <w:DoNotShowMarkup/> <w:DoNotShowComments/> <w:DoNotShowInsertionsAndDeletions/> <w:DoNotShowPropertyChanges/> <w:HyphenationZone>21</w:HyphenationZone> <w:PunctuationKerning/> <w:ValidateAgainstSchemas/> <w:SaveIfXMLInvalid>false</w:SaveIfXMLInvalid> <w:IgnoreMixedContent>false</w:IgnoreMixedContent> <w:AlwaysShowPlaceholderText>false</w:AlwaysShowPlaceholderText> <w:DoNotPromoteQF/> <w:LidThemeOther>EN-US</w:LidThemeOther> <w:LidThemeAsian>X-NONE</w:LidThemeAsian> <w:LidThemeComplexScript>X-NONE</w:LidThemeComplexScript> <w:Compatibility> <w:BreakWrappedTables/> <w:SnapToGridInCell/> <w:WrapTextWithPunct/> <w:UseAsianBreakRules/> <w:DontGrowAutofit/> <w:SplitPgBreakAndParaMark/> <w:EnableOpenTypeKerning/> <w:DontFlipMirrorIndents/> <w:OverrideTableStyleHps/> </w:Compatibility> <m:mathPr> <m:mathFont m:val="Cambria Math"/> <m:brkBin m:val="before"/> <m:brkBinSub m:val="&#45;-"/> <m:smallFrac m:val="off"/> <m:dispDef/> <m:lMargin m:val="0"/> <m:rMargin m:val="0"/> <m:defJc m:val="centerGroup"/> <m:wrapIndent m:val="1440"/> <m:intLim m:val="subSup"/> <m:naryLim m:val="undOvr"/> </m:mathPr></w:WordDocument></xml><![endif]--><!--[if gte mso 9]><xml> <w:LatentStyles DefLockedState="false" DefUnhideWhenUsed="true" DefSemiHidden="true" DefQFormat="false" DefPriority="99" LatentStyleCount="267"> <w:LsdException Locked="false" Priority="0" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Normal"/> <w:LsdException Locked="false" Priority="9" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="heading 1"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 2"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 3"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 4"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 5"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 6"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 7"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 8"/> <w:LsdException Locked="false" Priority="9" QFormat="true" Name="heading 9"/> <w:LsdException Locked="false" Priority="39" Name="toc 1"/> <w:LsdException Locked="false" Priority="39" Name="toc 2"/> <w:LsdException Locked="false" Priority="39" Name="toc 3"/> <w:LsdException Locked="false" Priority="39" Name="toc 4"/> <w:LsdException Locked="false" Priority="39" Name="toc 5"/> <w:LsdException Locked="false" Priority="39" Name="toc 6"/> <w:LsdException Locked="false" Priority="39" Name="toc 7"/> <w:LsdException Locked="false" Priority="39" Name="toc 8"/> <w:LsdException Locked="false" Priority="39" Name="toc 9"/> <w:LsdException Locked="false" Priority="35" QFormat="true" Name="caption"/> <w:LsdException Locked="false" Priority="10" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Title"/> <w:LsdException Locked="false" Priority="1" Name="Default Paragraph Font"/> <w:LsdException Locked="false" Priority="11" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Subtitle"/> <w:LsdException Locked="false" Priority="22" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Strong"/> <w:LsdException Locked="false" Priority="20" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Emphasis"/> <w:LsdException Locked="false" Priority="59" SemiHidden="false" UnhideWhenUsed="false" Name="Table Grid"/> <w:LsdException Locked="false" UnhideWhenUsed="false" Name="Placeholder Text"/> <w:LsdException Locked="false" Priority="1" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="No Spacing"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading Accent 1"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List Accent 1"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid Accent 1"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1 Accent 1"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2 Accent 1"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1 Accent 1"/> <w:LsdException Locked="false" UnhideWhenUsed="false" Name="Revision"/> <w:LsdException Locked="false" Priority="34" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="List Paragraph"/> <w:LsdException Locked="false" Priority="29" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Quote"/> <w:LsdException Locked="false" Priority="30" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Intense Quote"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2 Accent 1"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1 Accent 1"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2 Accent 1"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3 Accent 1"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List Accent 1"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading Accent 1"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List Accent 1"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid Accent 1"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading Accent 2"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List Accent 2"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid Accent 2"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1 Accent 2"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2 Accent 2"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1 Accent 2"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2 Accent 2"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1 Accent 2"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2 Accent 2"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3 Accent 2"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List Accent 2"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading Accent 2"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List Accent 2"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid Accent 2"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading Accent 3"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List Accent 3"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid Accent 3"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1 Accent 3"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2 Accent 3"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1 Accent 3"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2 Accent 3"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1 Accent 3"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2 Accent 3"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3 Accent 3"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List Accent 3"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading Accent 3"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List Accent 3"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid Accent 3"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading Accent 4"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List Accent 4"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid Accent 4"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1 Accent 4"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2 Accent 4"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1 Accent 4"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2 Accent 4"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1 Accent 4"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2 Accent 4"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3 Accent 4"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List Accent 4"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading Accent 4"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List Accent 4"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid Accent 4"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading Accent 5"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List Accent 5"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid Accent 5"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1 Accent 5"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2 Accent 5"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1 Accent 5"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2 Accent 5"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1 Accent 5"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2 Accent 5"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3 Accent 5"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List Accent 5"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading Accent 5"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List Accent 5"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid Accent 5"/> <w:LsdException Locked="false" Priority="60" SemiHidden="false" UnhideWhenUsed="false" Name="Light Shading Accent 6"/> <w:LsdException Locked="false" Priority="61" SemiHidden="false" UnhideWhenUsed="false" Name="Light List Accent 6"/> <w:LsdException Locked="false" Priority="62" SemiHidden="false" UnhideWhenUsed="false" Name="Light Grid Accent 6"/> <w:LsdException Locked="false" Priority="63" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 1 Accent 6"/> <w:LsdException Locked="false" Priority="64" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Shading 2 Accent 6"/> <w:LsdException Locked="false" Priority="65" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 1 Accent 6"/> <w:LsdException Locked="false" Priority="66" SemiHidden="false" UnhideWhenUsed="false" Name="Medium List 2 Accent 6"/> <w:LsdException Locked="false" Priority="67" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 1 Accent 6"/> <w:LsdException Locked="false" Priority="68" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 2 Accent 6"/> <w:LsdException Locked="false" Priority="69" SemiHidden="false" UnhideWhenUsed="false" Name="Medium Grid 3 Accent 6"/> <w:LsdException Locked="false" Priority="70" SemiHidden="false" UnhideWhenUsed="false" Name="Dark List Accent 6"/> <w:LsdException Locked="false" Priority="71" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Shading Accent 6"/> <w:LsdException Locked="false" Priority="72" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful List Accent 6"/> <w:LsdException Locked="false" Priority="73" SemiHidden="false" UnhideWhenUsed="false" Name="Colorful Grid Accent 6"/> <w:LsdException Locked="false" Priority="19" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Subtle Emphasis"/> <w:LsdException Locked="false" Priority="21" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Intense Emphasis"/> <w:LsdException Locked="false" Priority="31" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Subtle Reference"/> <w:LsdException Locked="false" Priority="32" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Intense Reference"/> <w:LsdException Locked="false" Priority="33" SemiHidden="false" UnhideWhenUsed="false" QFormat="true" Name="Book Title"/> <w:LsdException Locked="false" Priority="37" Name="Bibliography"/> <w:LsdException Locked="false" Priority="39" QFormat="true" Name="TOC Heading"/> </w:LatentStyles></xml><![endif]--><!--[if gte mso 10]><style> /* Style Definitions */ table.MsoNormalTable{mso-style-name:"Table Normal";mso-tstyle-rowband-size:0;mso-tstyle-colband-size:0;mso-style-noshow:yes;mso-style-priority:99;mso-style-parent:"";mso-padding-alt:0cm 5.4pt 0cm 5.4pt;mso-para-margin-top:0cm;mso-para-margin-right:0cm;mso-para-margin-bottom:8.0pt;mso-para-margin-left:0cm;line-height:107%;mso-pagination:widow-orphan;font-size:11.0pt;font-family:"Calibri","sans-serif";mso-ascii-font-family:Calibri;mso-ascii-theme-font:minor-latin;mso-hansi-font-family:Calibri;mso-hansi-theme-font:minor-latin;mso-ansi-language:EN-US;mso-fareast-language:EN-US;}</style><![endif]--></p><p>Luminescentni nanokristali (nanofosfori) na bazi fluorapatita (FAP-a) dopirani elementima retkih zemalja idealni su kontrastni agenti za bio-medicinske primene, kao &scaron;to su detekcije, snimanja, praćenja i terapije ćelija kancera. Kancer je jedna od najče&scaron;ćih bolesti modernog doba čiji uspeh lečenja zavisi od rane dijagnostike i neinvazivnog tretmana. Luminescentne nanočestice mogu uneti inovativnu paradigmu u lečenje kancera kombinovanjem biosnimanja, dijagnostike i tretmana. Za studije fluorescentnih biosnimanja nanokristali fluorapatita dopirani retkim zemljama kao kontrastni agenti pružaju značajne prednosti u vidu velikih kontrasta i dugotrajnosti luminescencije, i &scaron;to je jo&scaron; važnije visoke biokompatibilnosti, netoksičnosti i bioaktivnosti. Glavni ciljevi ove doktorske disertacije su sinteza novih luminescentnih multifotonskih bionanomaterijala na bazi fluorapatita dopiranih jonima prazeodimijuma (Pr³⁺), njihova karakterizacija i evaluacija&nbsp; primene za fluorescentna biosnimanja kancera. Sintezom nanoprahova u umerenim uslovima metodom ko-precipitacije, a potom su&scaron;enjem na 110 ^oC i kalcinacijom na temperaturama od 700 i 1000 ^oC očekuje se pronalaženje najboljih uslova za dobijanje novih nanofosfora koji bi na&scaron;li i različite bio-medicinske primene u oblasti fluorescentnih biosnimanja. Proučavane su tri vrste PrFAP nanokristala, sa 0,1%, 0,5% i 1% atomskih procenta Pr³⁺, zajedno sa nedopiranim FAP kontrolnim uzorkom. Nivoi energije aktivator jona Pr³⁺ sadrže metastabilna multipletna stanja koja nude mogućnosti efikasnih emisionih linija u vi&scaron;e boja u FAP nanokristalima, kao i u infracrvenoj i ultravioletnoj oblasti spektra. Metodom ko-precipitacije na sobnoj temperaturi (25 ^oC), a potom su&scaron;enjem na 110 ^oC, sintetisani su monofazni heksagonalni nanokristali PrFAPs nepravilnog sfernog oblika. Termičkom analizom sintetisanih uzoraka, na&nbsp;osnovu detektovanih temperaturnih opsega procesa dekarbonacije i dehidroksilacije, utvrđene su temperature kalcinacije od 700 i 1000 oC. Termička analiza i karakterizacija uzoraka su pokazale da Pr³⁺ joni dovode do stabilizacije FAP strukture na vi&scaron;im temperaturama, &scaron;to je pripisano unosu lantanoidnih jona sa specifičnim magnetnim osobinama u sistem i stvaranju jačih privlačnih sila sa O^2-anjonima. Nanokristali su&scaron;eni na 100 ^oC i kalcinisani na 1000 ^oC, zbog prisustva defekata kristalne re&scaron;etke koji zadržavaju emisiju Pr³⁺ jona, nisu pokazali luminescentne karakteristike od značaja za primene u medicinskim fluorescentnim biosnimanjima. Kalcinacijom uzoraka na 700 ^oC izrađen je novi tip aktiviranih fluorapatitnih nanokristala dopira / <p>Luminescent nanocrystals (nanophosphorus) based on fluorapatite (FAP) doped with rare earth elements are ideal contrast agents for biomedical applications such as cancer cell detection, imaging, tracking and therapy. Cancer is one of the most common diseases of the modern times whose success of the cure depends on early diagnosis and non-invasive treatment. Luminescent nanoparticles can bring an innovative paradigm into the treatment of cancer by combining bioimaging, diagnostics and treatment. Rare earth doped fluorapatite nanocrystals as contrast agents for studies of fluorescence bioimaging, offer significant advantages in terms of high contrasts and long-term luminescence, and more importantly high biocompatibility, non-toxicity and bioactivity. The main objectives of this doctoral dissertation are the synthesis of novel luminescent multiphoton bionanomaterials based on fluorapatites doped with praseodymium ions (Pr³⁺), their characterization and evaluation of their application for cancer fluorescence bioimaging. Synthesis of nanopowders under moderate conditions by the co-precipitation method, followed by dried at 110 &deg;C and calcination at 700 and 1000 &deg;C, is expected to find the best conditions for obtaining new nanophosphors that would find different bio-<br />medical applications in the field of fluorescence bioimaging. Three types of PrFAP nanocrystals were studied, with 0,1%, 0,5%, and 1% atomic percentages of Pr³⁺, together with an undoped FAP control sample. Energy levels of the Pr³⁺ ion activator contain metastable multiplet states that offer the possibility of efficient multi-color emission lines in FAP nanocrystals as well as in the infrared and ultraviolet regions of the spectrum. Single-phase hexagonal nanocrystals PrFAPs of irregular spherical shape were synthesized by the method of co-precipitation at room temperature (25 ^oC) and then drying at 110 ^oC. Thermal analysis of the synthesized samples, based on the detected temperature ranges of the decarbonation and dehydroxylation processes, determined calcination temperatures of 700 and 1000 ^oC. Thermal analysis with characterization showed that Pr³⁺ ions lead to stabilization of the FAP structure at higher temperatures,&nbsp;which was attributed to the entry of lanthanoid ions with specific magnetic properties into the system and the creation of stronger attractive forces with O^2- anions. Nanocrystals dried at 100 ^oC and calcined at 1000 ^oC, due to the presence of crystal lattice defects that quench the emission of Pr³⁺ ions, did not show luminescent characteristics of significance for applications in medical fluorescence imaging. Calcination of the samples at 700 ^oC produced a new type of activated praseodymium doped fluorapatite nanocrystals (PrFAPa) with excitation-emission profiles in the visible part of the spectrum. Physicochemical characterization confirmed spherical crystals of hexagonal structure up to a nanometer size of about 20 nm. Quantum-chemical calculations predicted that Pr³⁺ ions would be embedded in the crystal lattice of FAP nanocrystals at the Ca2 position (6h), which was followed by deformations of the F^- ion position. The assumed substitution mechanism is one Pr3+ ion for one Ca²⁺, with partial substitution of F^&ndash;anions with O^2&ndash; and OH^&ndash; and creation of vacancies due to achieving system neutrality. The results of in vitro biocompatibility and hemocompatibility showed that PrFAP nanocrystals were not toxic to living cells. In addition, the internalization of PrFAPa nanocrystals by skin (A431) and lung (A549) cancer cells was studied using fluorescence-based confocal microscopy and wide-field microscopy. The nanocrystals show characteristic green emission at 545 nm (³P₀&rarr;³H₅ transition of Pr³⁺ ion) and orange emission at 600 nm (¹D₂&rarr;³H₄), which we use to discriminate from cell autofluorescence. Studies of the images obtained by confocal microscopy in the blue, green, and red channels revealed that nanocrystals could recognize the cell surface and adhere to it, but they did not confirm the entry of nanocrystals into the cells. The wide-field microscopy detected emission transitions in green and orange color, and confirmed that the luminescent signal was coming from inside the cells. Using resonant excitation of PrFAP nanocrystals at 488 nm and emission of 600 nm, confocal microscopy extracted the fluorescence signal from inside the cancer cells. Orthogonal projections across 3D confocal stacks show that the nanocrystals are able to enter the cells positioning themselves within the cytoplasm. Overall, the obtained PrFAPa nanocrystals are biocompatible and of the tested types, the 0,5% Pr³⁺ doped nanocrystals show the highest promise as a tracking nanoparticle probe for bioimaging applications.</p>

No description available.

No / The latest advances in mesocrystal formation and non-classical crystallization of pre-synthesised nanoparticles have been reviewed with the focus on providing a fuller description of a number of complex systems and their properties and applications through examination of the crystallisation mechanisms at work. Two main crystallization principles have been identified; classical crystallization and particle based aggregation modes of non-classical pathways. To understand the non-classical pathways classical crystallization and its basics are introduced before non-classical pathways, such as oriented attachment and mesocrystal formation, are examined. In particular, the various destabilization mechanisms as applied to the pre-synthesized building blocks in order to form mesocrystalline materials as well as the interparticular influences providing the driving forces are analyzed and compared to the mechanisms at work within classical crystallization. Furthermore, the new properties of the mesocrystalline materials that derive from the collective properties of the nanoparticular building units, and their applications potential are presented. It is shown that this new class of materials has the potential to impact in a number of important areas such as sensor applications, energy conversion, photonic crystals as well as for energy storage, optoelectronics and heterogeneous catalysis or photocatalysis.

Les différentes lithologies sédimentaires du Groupe Belqa présentent un enrichissement en P et en toute une série d'éléments sensibles aux conditions redox. Il est montré que l'enrichissement en U, Cu, Co, Mo, V résulte d'un dépôt syn-sédimentaire sous conditions suboxiques. Par contre, les éléments Cr, Ni, Cd, Zn sont beaucoup plus enrichis et requierent un flux exogénique de métal probablement relié à l'altération de roches ultrabasiques obductées à la même période au nord de cette région, lors de la collision de la plaque arabo-africaine avec la plaque eurasienne. Les phosphates représentent le principal hôte de l'uranium et des terres rares. L'analyse des apatites par ablation laser ICP-MS a permis de montrer leur évolution, depuis le stade sédimentaire-diagénétique, puis pyrométamorphique, jusqu'à l'altération supergène. La libération de l'uranium de la structure de l'apatite lors du pyrométamorphisme et de l'altération supergène permet sa mise à disposition pour la formation de minéralisations. Le pyrométamorphisme, dû à une combustion des niveaux riches en matière organique, est responsable de la déstabilisation des apatites, et de la formation de roches de compositions semblables à des ciments clinker/Portland. L'uranium a également été libéré de la structure de l'apatite par altération supergène. L'altération météorique et les fluides évaporitiques ont permis le lessivage et le transport des éléments (U, V) des roches carbonatées métamorphiques, et des carbonates puis a conduit au dépôt des vanadates d'uranyles dans les carbonates pulvérulents ayant subi une dissolution importante / The different lithologies of the Belqa Group present an enrichment in P and various redox sensitive elements. The U, Cu, Co, Mo, V enrichment results from synsedimentary deposition in suboxic conditions. However, the higher Cr, Ni, Cd, Zn enrichment requires an exogenic metal flux probably related to the terrestrial leaching of ultrabasic rocks obducted during the collision between African-Arabian and Eurasian plates to the north of the study region, at the same time. Phosphates are the main host lithology for uranium and rare earth elements. The analysis of the apatites by laser ablation ICP-MS shows their evolution along the sedimentary-diagenetic and pyrometamorphic stages, up to the supergene weathering. The uranium liberation from the apatite structure during the pyrometamorphism and surficial weathering led to its availability as supergene ore mineralization. Pyrometamorphism resulted from the combustion of organic-rich layers and caused the destabilization of the apatites, and the formation of rocks which have compositions similar to clinker/Portland cements. Uranium has been also released from the structure of the apatite by supergene alteration. Meteoric weathering and the evaporitic groundwater resulted in the leaching and the transport of the elements (U, V) from the metamorphic carbonated hills, and from the surrounding permeable limestone which has undergone dissolution in the near surface zone