Alien Registration- Mannisto, Adam (Orneville Twp, Piscataquis County)

https://digitalmaine.com/alien_docs/8477/thumbnail.jp

Alien Registration- Mannisto, Venla (Orneville Twp, Piscataquis County)

https://digitalmaine.com/alien_docs/8478/thumbnail.jp

The Californians Against Sexual Exploitation (CASE) Act: A Case Study in Policy Advocacy

In any given year in the United States of America at least 100,000 domestic youth are sexually exploited through the commercial sex industry. Current national and state laws do not adequately protect these children from being groomed, pimped, and exploited over and over again in their young lives. A majority of these children are trafficked from, into or within the nation’s most populated state of California. In 2003 the FBI identified three of the country’s 13 high-­‐intensity child sex trafficking cities as being in California. The cycle of violence these children endure is not being brought to justice through the current systems in place. These systems rob youth of their childhoods and futures, increase trauma, criminalize, and throw children into increasingly vulnerable situations often at the mercy of their exploiters. This case study is an analysis of the Californians Against Sexual Exploitation (CASE) Act, the product of advocacy group California Against Slavery. The CASE Act seeks to increase penalties for sex traffickers in an effort to restore justice to the thousands of child victims who are not being protected by the laws currently in place

Korrosion orsakad av delikvescent ZnCl2 i förbränning av sidoströmmar

Utnyttjande av biomassa och sidoströmmar i energiproduktionen är ett alternativ att minska användningen av fossila bränslen och öka självförsörjningen av energi. Egenskaperna hos olika biomassor och sidoströmmar varierar mycket och beläggningar som bildas kan leda till flera utmaningar i deras användning. En av dessa utmaningar är den ökade mängden av hygroskopiska salter som kan bildas i förbränningsanläggningens kalla ända och förorsaka korrosion. I denna avhandling studerades en av dessa salters, zinkkloridens (ZnCl2), hygroskopiska egenskaper och hur saltet kan orsaka lågtemperaturkorrosion. Zinkkloridens delikvescenstemperatur vid 25 volymprocent vattenånga (vol% H2O) bestämdes genom att mäta saltets konduktivitet med kronoamperometri. Saltets korrosivitet på rostfritt stål (AISI 347) och kolstål (P235GH) studerades vidare både under och ovanför saltets delikvescenstemperatur. För att simulera förhållanden i kalla ändan av en förbränningsanläggning- användes en rörugn och syntetisk rökgas. En ånggenerator användes för att producera en jämn ström av vattenånga. Efter varje experiment analyserades proven gravimetriskt och korrosionsprodukterna analyserades med mikroskop och SEM-EDX. Delikvescenspunkten bestämdes vara 156 °C vid 25 vol% H2O, vilket motsvarar en relativ fuktighet på ca 5 %. Det konstaterades också att korrosionshastigheten är beroende på stålet och temperaturen vid förhållanden då delikvescens sker. Det rostfria stålet visade sig vara resistent emot korrosionen vid alla testade temperaturer, emedan kolstålet korroderade kraftigt. Korrosionshastigheten var högst vid den lägsta temperaturen (100 °C). Vid högre temperaturer var korrosionshastigheten lägre. Detta berodde på att ZnCl2 bildade ett salt med Zn/Cl molförhållandet ca 1, vilket indikerar bildning av ZnOHCl. Detta salt är inte lika hygroskopiskt som ZnCl2. På basis av resultaten kunde man dra slutsatsen att det rostfria stålet gav ett mycket bättre skydd gentemot korrosion orsakad av hygroskopiskt ZnCl2

CO2 Capture and Low-Temperature Release by Poly(aminoethyl methacrylate) and Derivatives

Poly(aminoethyl methacrylate) (PAEMA), poly-(ethylene oxide)-block-(aminoethyl methacrylate) (PEO-PAEMA), and their guanidinylated derivates, poly(guanidine ethyl methacry-late) (PGEMA) and poly(ethylene oxide)-block-(guanidine ethyl methacrylate) (PEO-PGEMA), were prepared to study their capabilities for CO2 adsorption and release. The polymers of different forms or degree of guanidinylation were thoroughly characterized, and their interaction with CO2 was studied by NMR and calorimetry. The extent and kinetics of adsorption and desorption of N-2 and CO2 were investigated by thermogravimetry under controlled gas atmospheres. The materials did not adsorb N-2, whereas CO2 could be reversibly adsorbed at room temperature and released by an elevated temperature. The most promising polymer was PGEMA with a guanidinylation degree of 7% showing a CO2 adsorption capacity of 2.4 mmol/g at room temperature and a desorption temperature of 72 degrees C. The study also revealed relations between the polymer chemical composition and CO2 adsorption and release characteristics that are useful in future formulations for CO2 adsorbent polymer materials.Peer reviewe

Guanidiinivälitteiset Typpiyhdisteiden Karboksylaatiot

Carbon dioxide (CO2) is a vital molecule for biological systems, but it also plays a major role in our modern society. Historically, CO2 is thought to be a relatively unreactive molecule. Recent kinetic measurements have demonstrated that CO2 is surprisingly electrophilic. In many cases, the absence of observable CO2 adducts is due to insufficient thermodynamic driving force. The literature section of this thesis covers the physical organic chemistry behind the reactivity of CO2. The reader is introduced to the interplay of electrophilicity and nucleophilicity relevant to the kinetics of CO2-adduct formation. Thermodynamical forces and their stabilizing aspects are then discussed. The structure and reactivity of zwitterionic CO2-adducts of N heterocyclic carbenes and related compounds is presented. These findings, are then contrasted with superbases, guanidines and amidines, and their reactivity with CO2. Nitrogen compounds, such as aliphatic amines, aromatic amines, and protic N-heteroaryls, are discussed regarding their reactivity with CO2 through illustrative mechanistic proposals and synthetic applications. These compound classes exhibit a remarkable increase in affinity towards CO2 in the presence of superbases. The central CO2-based synthetic strategies to cyclic carbamates are analyzed from a retrosynthetic point of view, elucidating their advantages and limitations. The common feature uniting all presented approaches is that an amine first reacts with CO2, forming a carbamate. This species is then synthetically manipulated to obtain the desired cyclic carbamates. The experimental section presents the author’s original publications and discusses the core findings within. In the first publication, aromatic amines and CO2 reacted regioselectively to form five-membered cyclic carbamates in good yields (av. 75%) catalyzed by 1,1,3,3-tetramethylguanidine (TMG). In the second publication, the mechanistic interplay between aromatic amines, TMG, and CO2 was studied. It was found that the aromatic amine and TMG pre associated, which was followed by concerted deprotonation and carboxylation. The TMG CO2 zwitterion was isolated, and it was shown to be a carboxylation agent though an indirect mechanism. In the third publication, protic N heteroaryls and superbases were found to form neutral pairs, but when exposed to CO2, ionic mixed carbamates formed. These were either stable, exchanging CO2 slowly, or fluxional, exchanging CO2 rapidly. Synthesis of indole O-alkyl carbamates was demonstrated using catalytic superbase. Finally, in the fourth publication, amino alcohols and CO2 were reacted to form five-, six-, and seven-membered cyclic carbamates. The method was suited for the synthesis of medicinally relevant bicyclic and spirocyclic compounds.Hiilidioksidi (CO2) on elintärkeä molekyyli biologisille järjestelmille, mutta sillä on myös tärkeä rooli nyky-yhteiskunnassamme. Historiallisesti CO2:n on ajateltu olevan suhteellisen heikosti reagoiva molekyyli. Viimeaikaiset kineettiset mittaukset ovat osoittaneet, että CO2 on yllättävän elektrofiilinen. Monissa tapauksissa CO2-adduktien havaitsemattomuus johtuu riittämättömistä termodynaamisista voimista. Tämän väitöskirjan kirjallisuusosio kattaa CO2:n reaktiivisuuden taustalla olevan fysikaalisen orgaanisen kemian. Lukijalle esitellään elektrofiilisyyden ja nukleofiilisyyden vuorovaikutus, joka on olennainen CO2-adduktin muodostumisen kinetiikassa. Seuraavaksi käsitellään termodynaamisia voimia ja niiden stabiloivia vaikutuksia. N-Heterosyklisten karbeenien ja näihin liittyvien yhdisteiden zwitterionisten CO2-adduktien rakenne ja reaktiivisuus esitellään. Kyseisiä löydöksiä verrataan superemäksiin, guanidiineihin ja amidiineihin sekä näiden reaktiivisuuteen CO2:n kanssa. Typpiyhdisteitä, kuten alifaattisia amiineja, aromaattisia amiineja ja proottisia N-heteroaryylejä, käsitellään liittyen näiden reaktiivisuuteen CO2:n kanssa hyödyntäen havainnollistavia mekanistisia ehdotuksia ja synteettisiä sovelluksia. Näillä yhdisteluokilla on huomattava lisäys affiniteetissa CO2:ta kohtaan superemästen läsnä ollessa. Keskeisiä CO2-pohjaisia synteettisiä strategioita syklisille karbamaateille analysoidaan retrosynteettisestä näkökulmasta selvittäen näiden edut ja rajoitukset. Kaikkia esitettyjä lähestymistapoja yhdistävä yhteinen piirre on, että amiini reagoi ensin CO2:n kanssa muodostaen karbamaatin. Tätä yhdisteluokkaa käsitellään synteettisesti, jotta saadaan haluttuja syklisiä karbamaatteja. Kokeellinen osio esittelee kirjoittajan alkuperäisiä julkaisuja ja käsittelee niiden ydinhavaintoja. Ensimmäisessä julkaisussa aromaattiset amiinit ja CO2 reagoivat regioselektiivisesti muodostaen viisirenkaisia syklisiä karbamaatteja hyvillä saannoilla (keskimäärin 75%) 1,1,3,3-tetrametyyliguanidiinin (TMG) katalysoimana. Toisessa julkaisussa tutkittiin aromaattisten amiinien, TMG:n ja CO2:n mekaanista vuorovaikutusta. Havaittiin, että aromaattinen amiini ja TMG esijärjestyivät, jota seurasi yhtaikainen deprotonaatio ja karboksylaatio. TMG CO2 zwitterioni eristettiin, ja sen osoitettiin toimivan karboksylointireagenssina epäsuoran mekanismin kautta. Kolmannessa julkaisussa proottisten N-heteroaryylien ja superemästen havaittiin muodostavan neutraaleja pareja, mutta kun ne altistettiin CO2:lle, muodostui ionisia sekakarbamaatteja. Nämä olivat joko stabiileja, jotka vaihtoivat hiilidioksidia hitaasti, tai fluksionaalisia, jotka vaihtoivat hiilidioksidia nopeasti. Indoli-O-alkyylikarbamaattien synteesi näytettiin toteen käyttämällä katalyyttistä superemästä. Lopuksi neljännessä julkaisussa aminoalkoholit ja CO2 saatettiin reagoimaan muodostaen viisi-, kuusi- ja seitsemänrenkaisia syklisiä karbamaatteja. Menetelmä soveltui lääketieteellisesti merkityksellisten bisyklisten ja spirosyklisten yhdisteiden synteesiin

Bioinspirerad oxidation av C-H-bindningar med järnkatalys

Litteraturgranskningen i denna pro gradu behandlar oxidation av inerta C-H-bindningar med järnbaserade icke-hemkomplex. Naturligt förekommande enzymers aktiva centrum har använts som inspiration vid utveckling av katalytiska komplex. Forskningsområdet har attraherat stort intresse en längre tid eftersom kemiindustrins utgångsämnen är huvudsakligen ofunktionaliserade kolväten som utvinns ur råolja. Ett stort genombrott gjordes år 2001 då det syntetiserades ett järnkomplex vars katalytiska cykel involverade en metallcentrerad FeV=O-oxidant. Kolväten oxiderades avsevärt effektivare jämfört med tidigare komplex som oxiderade substrat via fria radikaler. Sedan dess har utvecklingen skett snabbt. Det har bevisats att ligandgeometrin påverkar kraftigt den katalytiska aktiviteten. Komplex med cis-α-geometri har den bästa aktiviteten. Oxidationsselektiviteten baserar sig på sterisk växelverkan mellan substrat och ligand, samt elektroniska och stereoelektoniska egenskaper hos substratet. Dessa faktorer kan överskridas om substratet har en dirigerande karboxylsyra. Steriskt hindrade ligander förlänger den katalytiska livstiden och förbättrar oxidationsselektiviteten. Det har nyligen föreslagits en alternativ katalytisk cykel som involverar en FeIV=O-intermediär för komplex med en trigonal bipyramidstruktur. I framtiden kommer det att vara relevant att indela icke-hemkomplex i två olika undergrupper på basen av geometri och oxidationstillståndet av järn. I den experimentella delen presenteras syntesen för nya ligander. Dessa jämfördes med kommersiella ligander vid järnkatalyserad oxidation av etylbensen och cyklohexan. Oxidation av C-H-bindningar skedde enbart i närvaro av järn. Utbytet förbättrades varken av de nya eller kommersiella liganderna. Produktprofilen tydde inte på en metallcentrerad oxidant. Sannolikt bildades det långlivade alkylradikaler såsom i Gif-kemi

Selective Aerobic Oxidation of Alcohols with NO3‐ Activated Nitroxyl Radical/Manganese Catalyst System

A homogeneous Mn(NO3)(2)/2,2,6,6-tetramethylpiperidin-1-yl)oxyl/2-picolinic acid catalyst system is highly active and versatile for the selective aerobic oxidation of alcohols (2,2,6,6-tet-ramethylpiperidin-1-yl)oxyl = TEMPO, 2-picolinic acid = PyCOOH). The catalytic method enables near quantitative conversion of various primary alcohols to the respective aldehydes using a very simple reaction setup and workup. This study presents findings on the catalyst stability and mechanisms of deactivation. The results show that NO3- plays a crucial catalytic role in the reaction as a source of oxygen activating NOx species. Yet, disproportionation of NO3- to the volatile NO2 during the reaction leads to catalyst deactivation under open air conditions. Catalyst deactivation through this route can be overcome by adding a catalytic amount of nitrate salt, for example NaNO3 into the reaction. This stabilizes the Mn(NO3)(2)/TEMPO/PyCOOH catalyst and enables oxidation of various primary alcohols to the respective aldehydes using low catalyst loadings under ambient conditions. Secondary alcohols can be oxidized with a modified catalyst utilizing sterically accessible nitroxyl radical 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO) instead of TEMPO. At the end of the alcohol oxidation, pure carbonyl products and the reusable catalyst can be recovered simply by extracting with organic solvent and dilute aqueous acid, followed by evaporation of both phases.Peer reviewe

Association of the DBH Polymorphism rs3025343 With Smoking Cessation in a Large Population-Based Sample

Introduction: Genetic variations in DBH-gene and its surroundings have been shown to associate with smoking behavior including smoking cessation in several studies. In this study we replicate and measure the effect size for association between DBH polymorphism rs3025343 and smoking cessation in a large population-based sample while examining environmental factors that could relate to the association. Methods: We studied 11 926 adult subjects from four surveys of the National FINRISK Study. The analysis was restricted to either current or former smokers. Logistic and linear regression analyses were conducted to investigate the relationships of the single nucleotide polymorphism (SNP), covariates, smoking cessation, and smoking severity (cotinine, CPD). Gene-environment interactions were tested by likelihood-ratio test. Results: The association between rs3025343 and smoking cessation (prevalence odds ratio, OR = 1.12, p = .094, 95% CI = 0.98-1.30) was replicated identically with the GWAS study of The Tobacco and Genetics Consortium (OR = 1.12, 95% CI = 1.08-1.18). None of our tested phenotypes significantly influenced the association between rs3025343 and smoking cessation. Overall, marital status, education, depression, alcohol use, self-rated health, and chronic obstructive pulmonary disease (COPD) showed phenotypic associations with smoking cessation, but the association of various phenotypes with smoking cessation did not vary by genotype. Conclusions: The current study replicates the effect size for the association between rs3025343 and smoking cessation despite lack of overall significance due to smaller sample size. We could not show environmental influences on the association of rs3025343 with smoking cessation. Implications: Our study replicates the direction and strength of the association of DBH polymorphism rs3025343 with smoking cessation. We could not detect environmental influences on the strength of the association of rs3025343 with smoking cessation, but the limited power of our analysis needs to be taken into account.Peer reviewe